Abstract Book (V1)

th
The 4 Asia-Pacific Conference on Ionic

Liquids and Green Processes
and
The 6th Australasian Symposium on Ionic
Liquids
Sydney, Australia 2014
4th Asia-Pacific Conference on Ionic Liquids and Green Processes / 6th Australasian Symposium on Ionic Liquids (APCIL-4/ASIL-6 2014)
28th September - 1st October, 2014 Sydney Australia
Welcome!
It is great pleasure to welcome you to the combined 4th Asia Pacific Conference on Ionic Liquids
and Green Processes (APCIL) & 6th Australasian Symposium on Ionic Liquids (ASIL) in Sydney,
Australia.
APCIL was first held in 2008 in Beijing and the series has continued, with a conference being held
every two years ever since. APCIL is the major ionic liquid conference in Asia-Pacific region,
complementing the International Congress on Ionic Liquids (COIL) meeting.
The origin of ASIL can be dated back to 2003, initially intended as a locally run workshop in
Victoria, Australia. These ASIL meetings have attracted much interest in recent years from
attendees all over the Asia-Pacific region and are also run every other year. This year, for the first
time, the two conferences are combined together and held in Sydney, the largest city in New South
Wales and Australia.
The scientific topics of the combined APCIL-4/ASIL-6 2014 cover all aspects of ionic liquid
research, ranging from breakthroughs in fundamental research to progress in industrial applications.
The conference brings together scientific researchers and engineers to exchange ideas, present new
findings, and establish new collaborations. The conference is also designed to engage the next
generation of researchers, through opportunities for PhD students and early career researchers to get
involved in a scientific setting.
We would like to thank all participants, committee members and sponsors and student helpers for
their joint efforts on making this conference a very sucessful event.
Once again, welcome to Sydney and enjoy the adventure-rich city and its picturesque surroundings.
Chuan Zhao, Leigh Aldous and Jason Harper
The Organising Committee
Conference Organisers
A/Prof Chuan Zhao Chair, School of Chemistry, University of New South Wales, Australia
Dr Leigh Aldous Co-Chair, School of Chemistry, University of New South Wales, Australia
Dr Jason Harper Co-Chair, School of Chemistry, University of New South Wales, Australia
Local Organising Committee

Majid Asnavandi
Jeffrey Black
Bradley Butler
William Hart
Mengchen Ge
Christian Gunawan
Richard Gondosiswanto
Rebecca Hawker
Md. Mokarrom Hossain
Sinead Keaveney
Asim Khan
Benjamin Lau
Wuan Xin The
Trang To
International Advisory Committee

A/Prof Chuan Zhao (Co-Chair), University of New South Wales, Australia
Prof. Doug MacFarlane (Co-Chair), Monash University, Australia
Prof. Alan Bond, Monash University, Australia
Prof. Jason Clyburne, Saint Marys University, Canada
Prof. Richard G. Compton, University of Oxford, UK
Prof. Sheng Dai, Oak Ridge National Laboratory, USA
Prof. Youquan Deng, Lanzhou Institute of Chemical Physics, Chinese Academy of Science, China
Prof. Calum Drummond, RMIT University, Australia
Prof. Jairton Dupont, Universidade Federal do Rio Grande do Sul, Brazil
Prof. Frank Endres, Clausthal University of Technology, Germany
Prof. Rasmus Fehrmann, Technical University of Denmark, Denmark
Prof. Maria Forsyth, Deakin University, Australia
Prof. Buxing Han, Institute of Chemistry, Chinese Academy of Science, China
Prof. Mohd Ali Bin Hashim, University of Malaya, Malaysia
Prof. Patrik Johansson, Chalmers University of Technology, Sweden
Prof. Doseok Kim, Sogang University, Korea
Prof. Anil Kumar, National Chemical Laboratory, India
Prof. Jinghong Li, Tsinghua University, China
Prof. Peter Licence, University of Nottingham, UK
Prof. Lanqun Mao, Institute of Chemistry, Chinese Academy of Science, China
Prof. Thomas Maschmeyer, University of Sydney, Australia
A/Prof. Mohd Ibrahim Abdul Mutalib, Universiti Teknologi Petronas, Malaysia
Prof. Hiroyuki Ohno, Tokyo University of Agriculture & Technology, Japan
Prof. Colin Raston, Flinders University, Australia
Prof. Luis Paulo Rebelo, Instituto de Tecnologia Qumica e Biolgica, Portugal
Prof. Robin Rogers, University of Alabama, USA
Prof. Kenneth Seddon, Queens University Belfast, UK
Prof. I -Wen Sun, National Cheng Kung University, Taiwan
Prof. Peter Wasserscheid, Friedrich-Alexander-Universitt Erlangen-Nrnberg, Germany
Prof. Masayoshi Watanabe, Yokohama National University, Japan
Prof. Tom Welton, Imperial College London, UK
Prof. Suojiang Zhang, Institute of Process Engineering, Chinese Academy of Science, China
ii
Conference Programme at a Glance

Sunday 28th September
14:30
14:45
15:15
15:35
15:55
16:15
Title
Chair
17:00
17:15
17:30
17:45
18:00
OPENING REMARKS
15 min
Plenary session 1
Chair: Doug MacFarlane
P1 - Bond
K1 - Coutinho
K2 - Welton
K3 - Itoh
30 min
20
20
20
Coffee break
Parallel A session 1
Electrochemistry I
Pringle
A1 - Howlett
A2 - Rana
A3 - Kong
A4 - Rochefort
15 min
15
15
15
Drinks Reception
iii
45 min
Parallel B session 1
Separations
Coutinho
B1 - Weber
B2 -Li
B3 - Abdullah
B4 - Hadj-Kali
15 min
15
15
15
Until late

Monday 29th September
9:00
9:30
9:50
10:10
10:30
Title
Chair
11:15
11:30
11:45
12:00
12:15
13:20
13:50
14:10
14:30
14:50
Title
Chair
15:35
15:50
16:05
16:20
16:35
17:05
Plenary session 2
Chair: Greg Warr
P2 - Cheng (Jinpei)
K4 - Kim
K5 - Han
K6 - Izgorodina
30
20
20
20
Coffee break
Electrochemistry II
Howlett
A5 - Arrigan
A6 - Iliev
A7 - Ueda
A8 - Willert
15
15
15
15
45
Solvation and Structure I
Ohno
B5 - Fujita
B6 - Ma, Yingchong
B7 - Jiang
B8 - Wu, You-Ting
Lunch break
65
Plenary session 3
Chair: Chuan Zhao
P3 - Watanabe
K7 - Drummond
K8 - Warr
K9 - He
30
20
20
20
Coffee break
Materials
Dai
A9 - Priest
A10 - Zhang, Shiguo
A11 - Tian
A12 - Gupta
15
15
15
15
Poster-Flash
Poster Session
iv
15
15
15
15
45
Solvation and structure II
Atkin
B9 - Greaves
B10 - Yu
B11 - Huang
B12 - Shang
15
15
15
15
30
85

Tuesday 30th September
9:00
9:30
9:50
10:10
10:30
Title
Chair
11:15
11:30
11:45
12:00
12:15
13:20
13:50
14:10
14:30
14:50
Title
Chair
15:35
15:50
16:05
16:20
Plenary session 4
Chair: Damian Arrigan
P4 - Koo
K10 - Endres
K11 - Dai
K12 - Atkin
30
20
20
20
Coffee break
Biomass I
Welton
A13 - Simmons
A14 - Mu, Tiancheng
A15 - Kamimura
A16 - Yoshizawa-Fujita
15
15
15
15
45
Computational
Hunt
B13 - Xue
B14 - Tsuzuki
B15 - Abe
B16 - Sha
Lunch break
65
Plenary session 5
Chair: Leigh Aldous
P5 - Zhang
K13 - Fuchigami
K14 - Maschmeyer
K15 - Deng
30
20
20
20
Coffee break
Biomass II
Simmons
A17 - Byrne
A18 - Hummel
A19 - Anugwom
A20 - Zhuo, Kelei
15
15
15
15
15
15
15
15
45
Catalysis
Han
B17 - Henderson
B18 - Salimen
B19 - Liu, Ye
B20 - Liu, Zhimin
15
15
15
15
16:35
17:05
Poster-Flash
Poster Session
30
85
18:30
DINNER
Until late

Wednesday 1st October
9:00
9:30
9:50
10:10
Plenary session 6
Chair: Jason Harper
P6: Ohno
K16: Hunt
K17: Clyburne
K18: Chen
30
20
20
20
10:30
Coffee break
45
Title
Chair
11:15
11:30
11:45
12:00
Novel ionic liquids
Clyburne
A21 - Curnow
A22 -Chu
A23 - Mochida
A24 - Zhang, Rui
15
15
15
15
Electrochemistry III / Catalysis II
Chen, G. Z.
B21 - Pringle
15
B22 - Ruether
15
B23 - Matsumoto
15
B24 - Jain
15
12:15
CLOSING REMARKS
15
12:30
Final lunch
60
vi
The conference organisers would like to thank the following groups for their generous support:
The University of New South Wales, School of Chemistry
The Ian Potter Foundation
Io-Li-Tec, Ionic Liquid Technologies
ProDigital Pty. Ltd.
ARC Centre for Excellence for Electromaterials Science
vii
Getting to and from Coogee
viii
Poster Presentations - Monday 29th September

No.
Presenter
Institution
Title
M1
Leigh Aldous
University of New South

Wales
Biomass Processing of Rice Husks with Partially Hydrated

Hydroxides
M2
Danah Al-Masri
Deakin University
Increasing the efficiency of ionic liquid-based

thermoelectrochemical cells
M3
Ian Harvey
Arellano
University of South
Australia
M4
Arifin
Nagoya University
M5
Majid
Asnavandi

Wales
Electrodeposition of Pd-Sn Alloy Catalyst from Ionic Liquids

for Oxygen Reduction Reaction
M6
San Mei Bong
Deakin University
Bioethanol production from lignocellulose materials via the

combined use of ionic liquids and enzymes.
M7
Saffron J.
Bryant
University of Sydney
Compartmentalisation by Vesicles in Ionic Liquids
M8
Bradley J.
Butler

Wales
The effect of ionic liquids on reactions at phosphorus
M9
Diogo Cabral
Monash University
Electrochemistry of ionic liquids for redox flow battery

electrolytes
M10
Kun Chen
Monash University
Ordered Nanoporous Metals from Ionic Liquid Templates for

Sustainable Energy Applications
M11
Zhengfei Chen
University of Newcastle
Structure of PEO-PEGE Block Polyethers in

Ethylammonium Nitrate and Adsorbed to Silica
M12
Alison Chong
Monash University
Novel Multifunctional Organic Salts to Combat

Microbiologically Influenced Corrosion
M13
Peter K. Cooper
A low concentration of ionic liquid dissolved in base oil

lubricates as effectively as the pure ionic liquid
M14
Joo A. P.
Coutinho
University of Aveiro
Chlorophyll extraction from spinach using aqueous solutions

of ionic liquids
M15
Joo A. P.
Coutinho
University of Aveiro
Polarity control of aqueous biphasic systems using ionic

liquid mixtures
M16
Samuel
Cronshaw
Swelling of the Near-Surface Nanostructure of

Propylammonium Nitrate by Octanol Imaged Using
Amplitude-Modulated Atomic Force Microscopy
M17
Rasike De Silva
Deakin University
Use of ionic liquids for the separation of polyester/cotton

textile wastes: A complete recycling solution
M18
Andrew Dolan
H-bond capacity and self-assembly of cationic surfactants in

protic ionic liquids
Porous silica spheres-supported Zn-functionalized ionic

liquid as sorbents for CO2 capture
Glucose to 5-hydroxymethylfurfural
transformationin acidic aqueous and ionic liquid
solvents
ix
No.
Presenter
Institution
Title
M19
Max E Easton
The directed formation of high-order polybromides from

ionic liquids
M20
Aaron Elbourne
Nanostructure of Ionic Liquid-Solid Interfaces Revealed with

High Resolution Using Amplitude Modulated-Atomic Force
Microscopy
M21
Wei-Cheng Fu
National Cheng Kung

University
Electrochemical Preparation of Nanoporous poly

(3,4-ethylenedioxythiophene) on carbon substrate electrodes
from ionic liquid for supercapacitors
M22
Batchimeg
Ganbold
University of Western
Sydney
The effective charge of the cations and anions in EMIMFSA

ionic liquid studied by eNMR
Julin Garca
Complutense University of
Madrid
Isothermal vapor-liquid equilibria for ternary mixtures of

toluene and heptane with pure and mixed ionic liquids
involved in the aromatic extraction
M23
M24
Gaetan Girard
Deakin University
Role of the physicochemical properties of a

phosphonium-based ionic liquid on the interface and
performance of lithium battery electrodes
M25
Nicolas Goujon
Deakin University
Design of ion transport membranes using liquid crystalline

structured polymerizable ionic liquids
M26
Mariusz Grabda
Tohoku University
Prediction of effective ionic liquids extraction solvents by

COSMO-RS
M27
Christian
Gunawan

Wales
Robust and Versatile Ionic Liquids Microarray Achieved by

Microcontact Printing
M28
Kaihua Guo
Sun Yat-Sen University
Solubility of Carbon Dioxide in Aqueous Solution of

1-Aminopyl-3-Methylimidazolium Bromide with Hydrate
Formation
M29
Mohamed K.
Hadj-Kali
King Saud University
Solubility of CO2 in Ionic Liquids Analogous: Experiments

and Modeling
M30
Ahmed Halima
Monash University
Hydrogen Evolution at Semiconductor - Ionic Liquid

Interfaces
M31
William Hart

Wales
What effect does varying the anion and the cation of an ionic
liquid have on the dissolution of the different components of
biomass?
M32
Rebecca
Hawker

Wales
Novel chloroimidazolium-based ionic liquids: preparation,

characterisation and behaviour as solvents to control reaction
outcome
M33
Matthias Hilder
Deakin University
Low viscosity phosphonium-based ionic liquid for

electrolytes
M34
Hanee F.
Hizaddin
University of Malaya
Removal of nitrogen compounds for improved efficiency of

desulphurization of diesel using ammonium-based Deep
Eutectic Solvents
M35
Ashley Holding
University of Helsinki
Proton and HSCQ NMR of Cellulose and Wood in ionic

liquids
No.
Presenter
Institution
Title
M36
Hitoshi
Hosokawa
Kobe University
Ionic Liquids Containing Cationic Metal-Chelate Complexes

[ML1L2](Tf2N)
(M = CuII, NiII, PdII; L1 = diamine ligands; L2 = diketonate
ligands)
M37
Md. Mokarrom
Hossain

Wales
Catalyzed Lignin Depolymerisation using Polyoxometalate

Electrochemical Mediators in Ionic Liquids
M38
Md. Mokarrom
Hossain

Wales
Imidazolium-based Distillable Ionic Liquid for

Lignocellulosic Biomass Processing
M39
Michael
Hummel
Leopold-Franzens
University Innsbruck
High Yield Access to Imidazolium-based Fluorous Ionic

Liquids
M40
Takahiro
Ichikawa
Tokyo University of
Agriculture and Technology
Amino Acid Ionic Liquids as Self-organization Media of

Amphiphilic Molecules
M41
Boyan Iliev
Iolitec Ionic Liquids

Technologies
Electrolyte Systems and Interfacial Processes in Energy

Storage and Conversion
M42
Chaminda
Jayasinghe
University of Canterbury
Cellulose Dissolution and Regeneration Studies with

Triaminocyclopropenium Ionic Liquids
Pengju Ji
Tsinghua University
Absolute pKa Scales of Substituted Benzenethiols in Room

Temperature Ionic Liquids: An Unusual Solvation Effect
of Cation
M44
Yongzhong Jia
Qinghai Institute of Salt

Lakes, Chinese Academy of
Sciences
Extraction of lithium using ionic liquid dissolved in tributyl

phosphate
M45
Tao Jiang
Chinese Academy of
Sciences, Beijing
Ionic liquid promoted chemical fixation of CO2 to

quinazoline-2,4(1H, 3H)-diones
M46
Xinge Jiang
Zhengzhou University,
Effect of Amines on the Ionothermal Synthesis of AlPO4-5
M47
Sinead
Keaveney

Wales
Understanding and predicting organic reaction outcomes in

ionic liquids
M48
Asim Khan

Wales
Ionic Liquid-Based Mixed Electrolyte for High Performance

Rechargeable Li-O2 Batteries
M49
Doseok Kim
Sogang University
Gibbs monolayer of long-chain ionic liquids: halide-anion

effect and monolayer structure
M43
xi
Poster Presentations - Tuesday 30th September

No.
Presenter
Institution
Title
T1
Benjamin Boon
Yuen Lau

Wales
Extraction and electroanalytical quantification of capsaicin

and ascorbic acid from fresh chilli using ionic liquids
T2
Alexis Leblais
Deakin University
Preparation of polyacrylonitrilenatural polymer

composite precursors for carbon fiber using ionic liquid co
solvent solutions
Synthesis of Highly Luminescent N-doped Carbon Dots
T3
Haitao Li
Directly from an Ionic Liquid and Their Catalytic
Monash University
Application
An Ionic Liquid Lubricant Enables Superlubricity
to be Switched on in situ Using an Electrical
Potential
Synthesis of Novel Sodium-ion Conducting Poly-Ionic
Liquid Electrolytes
SO3H-functionalized Ionic Liquids Catalyzed Direct
Dehydrative Coupling of Alcohols or Alkenes with
Alcohols
T4
Hua Li
T5
Jiaye Li
Monash University
T6
Zhen Li
Chinese Academy of
Sciences, Lanzhou
T7
Zhiyong Li
Henan Normal University
Cinnamate-based Photoresponsive Ionic Liquids:

Synthesis and Photoresponsive Properties
T8
Hanming Liu
CSIRO Energy
Technology & University
of South Australia
Carbon Nanotube Supported Ionic Liquids for CO2

Capture
T9
Nai-Chang Lo
Kaohsiung Medical
University
Electrochemical Formation of Palladium Nanoparticles in

1-Butyl-1-Methylpyrrolidinium Salicylate Ionic Liquid
T10
Elena Lukoshko
Warsaw University of
Technology
Phase equilibria study of the binary systems of

[BMPYR]-based ionic liquids
T11
Elena Lukoshko
Warsaw University of
Technology
Activity coefficients at infinite dilution for organic solutes

and water in 1-butyl-3-methylpyridinium
tricyanomethanide ionic liquid
T12
T. Mandai
Yokohama National
University
Structure-Property Relationship of Glyme-Based Solvate

Ionic Liquids
T13
Samila McDonald
Structural Studies of Nanoscale Organic Hybrid Materials

for Carbon Capture
T14
Ciaran
McDonnell-Worth
Monash University
Low Overpotential Water Oxidation to Generate

Hydrogen Peroxide
T15
Ben McLean
Nanostructure of Glyme-based Solvate Ionic Liquids at

the Graphite Interface as a Function of Potential
T16
Xianghai Meng
China University of
Petroleum
Solubility Determination in Ionic Liquids Using In-Situ IR
xii
No.
Presenter
Institution
Title
T17
Siti Aminah Mohd

Noor
Monash University &

National Defence
University of Malaysia
Gel-Ionic Liquid Based Sodium Ion Conductors for

Sodium Batteries
T18
HeeJoon Moon
Yokohama National
University
Reversible Li-Intercalation into Graphite in Lithium

Solvate Ionic Liquids
T19
Thomas Murphy
Bulk Nanostructure of an Ionic Liquid glycerol mixture
T20
Mercedes Oliet
Complutense University of
Madrid
Saccharification of Eucalyptus globulus by BmimCl

dissolution
T21
Alister J. Page
3-Dimensional Nanostructure at the Graphite Protic

Ionic Liquid Interface
T22
Paulina Papis
University of Warsaw
Liquid phase behavior of binary mixtures containing ionic

liquids and molecular solvents
T23
Chang-jun Peng
East China University of

Science and Technology
The Synthesis of Anionic Metal Complex Ionic Liquids

and the Application in Carbon Dioxide Capture
T24
Kirankumar
Rajendranath
Kaohsiung Medical
University
Electropolymerized carbazole-containing ionic liquid in

the electrochemical determination of bio-molecules
T25
Vijayaraghavan
Ranaganthan
Monash University
Non-stoichiometric protic ionic liquids for enhanced CO2

absorption
T26
Anthony Rosamilia
CSIRO Energy
Technology
Anion Stabilisation by Intra-anionic Hydrogen Bonding

for Low Viscosity Ionic Liquids
T27
Anthony Rosamilia
CSIRO Energy
Technology
Magnetic Ionic Liquids Based on

Bis(trifluoromethanesulfonyl)imide Anion
T28
Anthony Rosamilia
CSIRO Energy
Technology
Phenolate Ionic Liquids for CO2 Post Combustion Capture
T29
Laura Sanchez
Deakin University
Ionic liquid electrolytes for the efficient recovery of

Neodymium from spent NdFeB magnets
T30
Thomas Rther
CSIRO Energy
Technology
Chelato Borate Low Temperature Molten Salts derived

from Pyrrolidinium Borohydride and their Application in
Battery Electrolytes
T31
Qunfeng Shao
Lanzhou University
A Method Based on Molecular Dynamics Simulation to

Calculate the Nonlinear Susceptibility of the Ionic Liquid
3-ethyl-1-methylimidazolium nitrate
T32
Chung-Jui Su
National Cheng Kung

University
Speciation and coordination of cobalt-chloride-based ionic

liquids
T33
Chung-Jui Su
National Cheng Kung

University
Fabricating nanostructured metals and alloys from Lewis

acidic metal-chloride based ionic liquids
T34
James Sweeney
Structural Effects on the Nanoscale Friction Responses of

Protic Ionic Liquids
T35
Wuan-Xin Teh

Wales
Developing Efficient Thermoelectrochemical Systems

with Ferrocene-based Ionic Liquid Electrolytes
xiii
No.
Presenter
Institution
Title
T36
Takahiro Ueda
Kobe University
Preparation and Properties of Ionic Liquids from Cationic

Ruthenocene Complexes with Trialkoxybenzene Ligands
T37
Kazuhide Ueno
Yokohama National
University
Ionic Effects of Glyme-Li Salt Solvate Ionic Liquids on

Performance of Next Generaion Batteries
T38
Yogendra Lal
Verma
Banaras Hindu University
Studies on Ultrasonic Assisted Synthesis of Ionic Liquid

Confined Porous Silica Gel Matrices
T39
Jian Wang
University of Chinese
Academy of Sciences
Efficient SO2 Capture through Ether-functionalized

Pyridinium Ionic Liquids
T40
Antony J. Ward
Facile, High-Yielding Synthesis of Pyrrolidinium,

Piperidinium, Morpholinium and
2,3-Dihydro-1H-isoindolinium Ionic Liquids From
Secondary Amines
T41
Kailas L. Wasewar
Visvesvaraya National
Institute of Technology
(VNIT) Nagpur
Deep Desulfurization Using Ionic Liquids For Low Sulfur

Liquid Fuel
T42
Guor-Tzo Wei
National Chung Cheng

University
Polymerized ionic liquid as a medium of chemical

modified electrodes for mediated electroanalysis
T43
Emmy C. Wijaya
University of Melbourne
and CSIRO Materials
Science and Engineering
The study of protein stability in Protic Ionic Liquids

(PILs) and molecular solvents
T44
Ross J. Wood
Influence of Alkyl Chain Length and Anion Species on

Ionic Liquid Structure at the Graphite Interface as a
Function of Applied Potential
T45
Haihong Wu
East China Normal

University
A Novel Brnsted Acidic Heteropolyanion-based Catalyst

for Synthesis of Tributyl Citrate Assisted by Microwave
Irradiation
T46
Feng Xin
CSIRO Energy
Technology & China
University of Mining and
Technology
Adsorption and Diffusivity of CO2 in Phosphonium Ionic

Liquid Modified Silica
T47
Yung-Che Yen
National Cheng Kung

University
Synthesis and Characterizations of Novel Ether Bridge

Based
Dicationic Ionic Liquids
T48
Zhi-Wu Yu
Tsinghua University
Hydrogen-Bonding Interactions between a Nitrile

Functional Ionic Liquid and Dimethyl Sulfoxide
T49
Ruhamah Yunis
University of Canterbury
Synthesis, Properties and Applications of Chiral Amino

Acid Ionic Liquids (CAAILs) based on
Triaminocyclopropenium Salts
T50
Dongsheng Zhang
Hebei University of
Technology
Hydrolysis of cyclohexanone oxime in SO3H-functional

ionic liquid
Xiangping Zhang
Academy of Sciences,
Beijing
CFD simulation on mass transfer properties of CO2

bubbles in ionic liquids
T51
xiv
No.
Presenter
Institution
Title
T52
Xiangping Zhang
Beijing
Efficient SO2 Capture through Ether-functionalized

Pyridinium Ionic Liquids
T53
Xiangping Zhang
Beijing
Techno-Environmental Analysis of Ionic Liquids

Scrubbing processes for Biogas Upgrading
T54
Ce Zhang
Yokohama National
University
Stability of Solvates and Electrochemical Properties of

Solvate Ionic Liquids
T55
Kelei Zhuo
Henan Normal University
Response of a new multi-walled carbon nanotubes

modified carbon paste electrode to
1-hexyl-3-methylimidazolium cation in aqueous solutions
xv
Plenary Lectures
Nuances of Voltammetry in Ionic Liquids

Alan M. Bonda,*,
a
School of Chemistry, Monash University, Melbourne, Victoria 3800, Australia

* alan.bond@monash.edu
Ionic liquids provide a fascinating environment for dynamic electrochemical studies because the
medium simultaneously provides both the solvent and supporting electrolyte, in contrast to the
situation prevailing in organic solvents where electrolyte has to be deliberately added. This
difference introduces fascinating nuances into the theory of voltammetry in ionic liquids. The broad
base of new features introduced with respect to mass transport in terms of diffusivity, additively of
faradaic and non- faradaic currents, and double layer considerations will be briefly reviewed in this
lecture along with provision of a more detailed discussion of specific themes summarised below
that have important applied consequences.
(a) Principles and Applications of Voltammetry of Adhered Microparticles in Contact with Ionic
Liquids. In this topic, advantages provided by exploitation of the property frequently encountered in
which electroactive compounds have a high thermodynamics level of solubility in ionic liquids, but
a very slow rate of dissolution, will be considered. Under these circumstances, voltammetric studies
with adhered microparticles can be advantageously undertaken, allowing parameters such as formal
potentials, electrode kinetics of electroactive species and kinetics of chemical reactions coupled to
electron transfer to be investigated without lengthy and tedious solution preparation. Theoretical
aspects of analysis of data under these conditions will be presented.
(b) Application of Semiintegral and Convolution Voltammetry in Ionic Liquids. Steady-state
voltammetric techniques can provide advantages over transient ones in studies of mass transport in
conventional solvents because the steady-state limiting current, in contrast to the transient peak
current, is insensitive to both sluggish heterogeneous electron transfer kinetics and uncompensated
resistance. However, the intrinsically high viscosity of most room temperature ionic liquids makes
it difficult to approach a voltammetric steady-state, restricting the use of microelectrode, rotating
disk electrode and related methods in ionic liquid media. Semiintegral voltammetry, which allows
the mathematical transformation of the transient, peak shaped voltammogram obtained when
mass-transport occurs by semi-infinite planar diffusion into a form which closely resembles a
steady-state voltammogram, is shown to provide a powerful strategy to avoiding limitations
imposed by lack of access to steady state regimes in ionic liquid studies. This technique achieves
the same advantages as found with experimentally based steady-state techniques, but is based on
use of data derived under the transient conditions that almost invariably apply in viscous ionic
liquid media. An extension of this technique, known generally as convolution voltammetry, allows
this approach to be used under conditions where mass-transport by non-planar (radial) diffusion is
significant, thereby facilitating the use of a wide range of electrode geometries and scan rates.
Studies described in this lecture were undertaken in collaboration with members of the Monash Electrochemistry
Group and other colleagues. Their contributions along with financial support from the Australian Research Council are
gratefully acknowledged.
P1
Towards Energetic Guidelines in Ionic Media: The Standard pKa Scales in

Room-Temperature Ionic Liquids
Jin-Pei Chenga, b *
a
State Key Laboratory of Elemento-organic Chemistry, Collaborative Innovation Center of Chemical Science and
Engineering (Tianjin), and College of Chemistry, Nankai University, Tianjin 300071, China
b
Center of Basic Molecular Science and Department of Chemistry, Tsinghua University, Beijing 100084, China
*chengjp@nankai.edu.cn, jinpei_cheng@mail.tsinghua.edu.cn
Chemical transformation in neat ionic liquid involves breaking and reorganizing relevant chemical
bond in a charged micro-environment that is dramatically different from the conventional molecular
solvent. Consequently, unexpected chemistry is frequently observed when ionic liquid serves as the
reaction medium. Hence, care must be taken when applying the existing guiding principles in
literature, derived entirely from the studies in molecular solvents, to interpret or to predict the
chemical phenomena in ionic media. For instance, the absolute pKa values of benzoic acid in aprotic
molecular solvent DMSO (!: 46.7), acetonitrile (!: 35.7), and in aprotic ionic liquid BmimNTf2 (!:
11.5) are 11.0[1a], 21.5[1b], and 15.15[1c], respectively. This acidity order would not be anticipated
using the guideline based on dielectric constant ! though it is proven to be highly reliable for the
judgment of polar processes in molecular media. This implies that the knowledge of bond
energetics (pKa , BDE, etc.) in ionic liquid, the key factor to assess the internal thermodynamic
driving force of a chemical reaction, may not be directly extrapolated from the current
understanding of solution chemistry and thus indicates the immediate need of special research
attention in this regard.
Recently, it is encouraging to note that increasing attention is steadily accumulating towards
understanding the fundamentals of ionic liquid chemistry with special focus on acid-base
interactions.[2] In line with our years efforts on bond energies in molecular solvents[3], we have now
extended a systematic research to bond energetics in ionic liquid system.[1c,3] Till present, the
absolute pKa scales of the C-H, O-H, S-H, and N-H families of organic acids in four pure aprotic
ionic lquids have been established under standard conditions. This report will summarize these
works and discuss the stimulating findings in relation to the fascinating solvation effect of ionic
liquids,
* The author representing all coworkers of the work: Drs. Hui Deng Ha, Wang Za, Wang Z Da, Ji P Jb, Li Xa, and Xue X
S a.
References:
[1] a) Bordwell F G, Acc. Chem. Soc. 1988, 21, 456. b)!Ktt A, Leito I, et al., J. Org. Chem. 2006, 71, 2829. c) Wang Z,
Deng H, Li X, Ji P J, Cheng J-P, J. Org. Chem. 2013, 78, 12487.
[2] For examples, see: a) Thomazeau C, Olivier-Bourbigou H, Magna L, Luts S, Gilbert B, J. Am. Chem. Soc. 2003,
125, 5264. b) DAnna F, Vitale P, Noto R, J. Org. Chem. 2009, 74, 6224. c) Brhdadi R, Troupel M, Comminges C,
Laurent M, Doherty A P, J. Phys. Chem. B 2012, 116, 277. d) Shukla S. K, Kumar A, J. Phys. Chem. B 2013, 117,
2456.
[3] For examples, see: a) Cheng J-P, Xian M, Wang K, Yin Z, Zhu X, Wang P G, J. Am. Chem. Soc. 1998, 120, 10266.
b) Cheng J-P, Liu B, Zhao Y, et al., J. Am. Chem. Soc. 2000, 122, 9987. c) Zhu X Q, Li Q, Hao W, Cheng J-P, J.
Am. Chem. Soc. 2002, 124, 9887. d) Zhu X-Q, Zhang M, Yu A, Wang C, Cheng J-P, J. Am. Chem. Soc. 2008 , 130,
2501.
[4] a) Deng H, Li X, Chu Y, He J Q, Cheng J P, J. Org. Chem. 2012, 77, 7291. b) Xue X, Yang C, Li X, Cheng J-P,
Org. Chem. Front. 2014, 1, 176.
P2
Towards Energetic Guidelines in Ionic Media: The Standard pKa Scales in

Room-Temperature Ionic Liquids
Jin-Pei Chenga, b *
a
b
*chengjp@nankai.edu.cn, jinpei_cheng@mail.tsinghua.edu.cn
Chemical transformation in neat ionic liquid involves breaking and reorganizing relevant chemical
bond in a charged micro-environment that is dramatically different from the conventional molecular
solvent. Consequently, unexpected chemistry is frequently observed when ionic liquid serves as the
reaction medium. Hence, care must be taken when applying the existing guiding principles in
literature, derived entirely from the studies in molecular solvents, to interpret or to predict the
chemical phenomena in ionic media. For instance, the absolute pKa values of benzoic acid in aprotic
molecular solvent DMSO (!: 46.7), acetonitrile (!: 35.7), and in aprotic ionic liquid BmimNTf2 (!:
11.5) are 11.0[1a], 21.5[1b], and 15.15[1c], respectively. This acidity order would not be anticipated
using the guideline based on dielectric constant ! though it is proven to be highly reliable for the
judgment of polar processes in molecular media. This implies that the knowledge of bond
energetics (pKa , BDE, etc.) in ionic liquid, the key factor to assess the internal thermodynamic
driving force of a chemical reaction, may not be directly extrapolated from the current
understanding of solution chemistry and thus indicates the immediate need of special research
attention in this regard.
Recently, it is encouraging to note that increasing attention is steadily accumulating towards
understanding the fundamentals of ionic liquid chemistry with special focus on acid-base
interactions.[2] In line with our years efforts on bond energies in molecular solvents[3], we have now
extended a systematic research to bond energetics in ionic liquid system.[1c,3] Till present, the
absolute pKa scales of the C-H, O-H, S-H, and N-H families of organic acids in four pure aprotic
ionic lquids have been established under standard conditions. This report will summarize these
works and discuss the stimulating findings in relation to the fascinating solvation effect of ionic
liquids,
* The author representing all coworkers of the work: Drs. Hui Deng Ha, Wang Za, Wang Z Da, Ji P Jb, Li Xa, and Xue X
S a.
References:
[1] a) Bordwell F G, Acc. Chem. Soc. 1988, 21, 456. b)!Ktt A, Leito I, et al., J. Org. Chem. 2006, 71, 2829. c) Wang Z,
Deng H, Li X, Ji P J, Cheng J-P, J. Org. Chem. 2013, 78, 12487.
[2] For examples, see: a) Thomazeau C, Olivier-Bourbigou H, Magna L, Luts S, Gilbert B, J. Am. Chem. Soc. 2003,
125, 5264. b) DAnna F, Vitale P, Noto R, J. Org. Chem. 2009, 74, 6224. c) Brhdadi R, Troupel M, Comminges C,
Laurent M, Doherty A P, J. Phys. Chem. B 2012, 116, 277. d) Shukla S. K, Kumar A, J. Phys. Chem. B 2013, 117,
2456.
[3] For examples, see: a) Cheng J-P, Xian M, Wang K, Yin Z, Zhu X, Wang P G, J. Am. Chem. Soc. 1998, 120, 10266.
b) Cheng J-P, Liu B, Zhao Y, et al., J. Am. Chem. Soc. 2000, 122, 9987. c) Zhu X Q, Li Q, Hao W, Cheng J-P, J.
Am. Chem. Soc. 2002, 124, 9887. d) Zhu X-Q, Zhang M, Yu A, Wang C, Cheng J-P, J. Am. Chem. Soc. 2008 , 130,
2501.
[4] a) Deng H, Li X, Chu Y, He J Q, Cheng J P, J. Org. Chem. 2012, 77, 7291. b) Xue X, Yang C, Li X, Cheng J-P,
Org. Chem. Front. 2014, 1, 176.
P3
Enzymatic reactions in ionic liquids: structural dynamics and QSAR based

prediction
Yoon-Mo Koo* and Ngoc Lan Mai
Department of Biological Engineering, Inha University, Incheon, Republic of Korea
*ymkoo@inha.ac.kr
The potential of ionic liquids as green alternatives to environmentally harmful volatile organic
solvents in enzymatic reactions has been well recognized. However, choosing proper ionic liquid
for a specific enzymatic reaction (e.g. lipase catalyzed reactions) is a challenging task. In this
presentation, molecular dynamic simulation and quantitative structure-activity relationship (QSAR)
are considered as tools for selecting optimal ionic liquids for lipase-catalyzed reactions. First of all,
the conformational structure changes of Candida antarctica lipase B (CALB) in organic solvents
and ionic liquids observed by molecular dynamic simulation are discussed. The results
demonstrated that the conformational changes of the active site cavity are directly related to enzyme
activity and decreased in the following order: [Bmim][TfO] > tert-butanol > [Bmim][Cl]. The
entrance to the cavity is modulated by two isoleucines, ILE-189 and ILE-285, one of which is
located on the !-10 helix. The !-10 helix can substantially change its conformation due to specific
interactions with solvent molecules. This change is acutely evident in [Bmim][Cl] where
interactions of LYS-290 with chlorine anions caused a conformational switch between !-helix and
turn. Disruption of the !-10 helix structure results in a narrow cavity entrance and, thus, reduced the
activity of CALB in [Bmim][Cl]. Moreover, electrostatic energy between solvents and CALB is
correlated with the structural changes leading to differences in enzyme activity[1]. Secondly, QSAR
model using structural information of ionic liquids (molecular descriptors) was proposed to predict
the performance of enzymatic reaction in ionic liquids. For instance, COSMO-RS screening charge
density distribution ("-profile) of ionic liquids was used as numerical molecular descriptors to
establish the QSAR models for predicting the activity and enantioselectivity of lipase from Candida
antarctica and Rhizomucor miehei in the kinetic resolution of (R,S)-1-phenylethanol with vinyl
acetate in ionic liquids. The results showed that "-profile of ionic liquids could be used as an
excellent independent variable for predicting enzymatic reactions in ionic liquids. The nonlinear
QSAR models based on artificial neural networks methods showed better predictive ability (R2 >
0.91) than linear QSAR models based on multiple linear regression methods[2]. The results above
indicate that molecular dynamic simulation and QSAR model could be used for selecting/screening
optimal ionic liquids for enzymatic reactions.
References
[1] Kim HS, Ha SH, Sethaphong L, Koo Y-M, Yingling YG, Phys. Chem. Chem. Phys., 2014, 16: 2944-2953.
[2] Mai NL, Koo Y-M, Biochem. Eng. J., 2014 (accepted)
P4
Z-Bond and Meso-Structure of Ionic Liquids

Suojiang Zhang*, Kun Dong, Shimou Chen, Xiaomin Liu, Xiangping Zhang, Qian Wang
Beijing Key Laboratory of Ionic Liquids Clean Process, State Key Laboratory of Multiphase Complex System, Institute
of Process Engineering, Chinese Academy of Sciences, Beijing, China
*sjzhang@ipe.ac.cn
Ionic liquids (ILs) have emerged as a promising alternative to be catalyst/solvent due to unique
properties, like negligible volatility, high stability, higher solubility/selectivity, and tenability which
allows design of task-specific ILs. The key of designing suitable ILs is to understand the
relationship of the micro-structures of ILs and the properties. Unlike organic solvents/water, it is the
Z-bond and the aggregations of ILs that cause their remarkable properties.
The hydrogen-bond (H-bond) interactions in ILs have been described by conventional H-bond, i.e.,
A-HB. Coupling the strong electrostatic force, however, the H-bond between cation and anion
shows particular features from geometric, energetic, electronic and dynamic aspects, which is
inherently different from the conventional H-bond. This coupling interaction is defined here as
Z-bond, and the general model could be expressed as [A-HB] (A and B are heavy atoms,
and outside [] represent the charges of the cation containing A atom and anion containing B atom,
respectively). The new model could be generally used to describe the interactions in ILs, as well as
bio-systems involving in ions, ionic reaction and ionic materials. Moreover, it is Z- bond that
resulted in the aggregation or cluster of ILs, which may change the traditional view on ILs as the
homogeneous systems, and been the key feature in interpreting many physical phenomena. We have
performed the molecular dynamics (MD) simulations on a series of imidazolium and phosphonium
based ILs, and ionic clusters were found in such ILs and the microheterogeneity in imidazolium
amino acid ILs. The cluster structures were found in series of ILs through small angle X-ray
diffraction, NMR, surface tension and electrical conductivity. Furthermore, scale-up of ionic
liquid-based process requires the deep understanding of the fluid dynamic behavior and mass
transfer properties. The macroscopic effect of the clusters caused by Z-bond on the bubble size
distribution, gas holdup, diameter and interfacial area were analyzed by a high speed image pick-up
system and CFD. Based on the rigorous thermodynamic models, the process simulation was
conducted to determine the operational parameters and flowsheet structure.
The fundamental studies described above greatly support the development of ILs-enhanced green
technologies: 1) A pilot plant of cleaner process of MMA with 100,00 ton/a was built using ILs to
absorb MAL instead of methanol, demanding lower energy and investments; 2) IL catalyst was
synthesized and applied in a new EG/DMC process and a pilot plant is being constructed; 3) a
8000,000 Nm3/a NH3 recovery pilot plant was established with 30% reduction of energy demand
compared with water washing method; 4) The new generation of lithium battery electrolyte with
ILs has been produce with the scale of 500 ton/a. These applications have proved the industrial
feasibilities of the ILs, and also show their promising application prospects in the future.
P5
Functionalisation of ionic liquids realised by the control of

hydrophobicity/hydrophilicity balance
Hiroyuki Ohnoa,b
a
Department of Biotechnology, Tokyo University of Agriculture and Technology, Koganei, Tokyo184-8588, Japan
b
Functional Ionic Liquid Laboratories, Graduate School of Engineering,
Tokyo University of Agriculture and Technology
*ohnoh@cc.tuat.ac.jp
Ionic liquids are composed of only ions, and they are accordingly hygroscopic. Solubility of the
ionic liquids in water decreased by increasing hydrophobicity of the component ions. There are
other interesting properties of ionic liquids induced by the control of hydrophobicity/hydrophilicity
balance of the component ions.
Ionic liquids are roughly classified into two groups such as water-soluble and water-insoluble from
viewpoint of hydrophobicity. However, there is the third group in between them. Ionic liquids
having moderate hydrophobicity showed lower critical solution temperature (LCST)-type phase
behaviour with water[1,2]. They are miscible with water at low temperature and phase separated at
high temperature. Hydrophobicity/hydrophilicity balance of ion pair was strongly suggested to
control the phase behaviour, and the phase transition temperature was also the function of
concentration of ionic liquids in water and added microions[3]. This reversible phase change was
applied to separate water-soluble proteins[1] and expected to be novel reaction medium.
Another challenge is the design of polar and hydrophobic ionic liquids. It is generally well known
that polar molecules are always hydrophilic. However it is not easy to design polar and
hydrophobic molecules, we have tried to prepare this kind of ionic liquid through the task-sharing
of ions. By combining hydrophobic cation with polar anion, we succeeded to prepare the ionic
liquids with wished properties[4]. They will be used to dissolve target materials such as cellulose
keeping phase separation state with water. This should lead the hydrolysis of cellulose which was
extracted from biomass under the presence of minimum and constant amount of water.
Some other examples of functionalisation of ionic liquids through the control of
hydrophobicity/hydrophilicity balance of the component ions will also be mentioned at the talk.
References
[1] Y. Kohno, S. Saita, K. Murata, N. Nakamura, and H. Ohno, Polym. Chem., 2011, 2, 862-867.
[2] Y. Kohno, H. Arai, S. Saita, and H. Ohno, Australian J. Chem., 2011, 64, 1560-1567.
[3] S. Saita, Y. Kohno, and H. Ohno, Chem. Commun., 2013, 49, 93-95.
[4] Y. Fukaya and H. Ohno, PCCP, 2013, 15, 4066-4072.
P6
Keynote Lectures
pH-reversible ionic liquids based aqueous biphasic systems

Ana M. Ferreiraa, Ana M. Fernandesb, Robin D. Rogersc, Mara G. Freirea and Joo A. P. Coutinhoa,*
a
Chemistry Department, CICECO, University of Aveiro, Aveiro, Portugal

Chemistry Department, QOPNA Unit, University of Aveiro, Aveiro, Portugal
c
Center for Green Manufacturing and Department of Chemistry, The University of Alabama, Tuscaloosa, USA
*jcoutinho@ua.pt
b
Recently, dynamic and reversible biphasic systems constituted by ionic liquids (ILs) were revealed
to be potential extraction systems [1]. It was previously demonstrated that mixtures involving ILs
and other solvents can be switched between the homogeneous regime and a two-phase system either
by a temperature-driven phenomenon or by adding CO2/N2 [1]. These systems have shown to be
highly valuable in the separation field, for instance in the separation of proteins.[1]
Amongst the liquid-liquid extraction techniques, aqueous biphasic systems (ABS) constitute a
greener and more benign and biocompatible option since they are mainly composed of water (ca.
50 wt%). In spite of all the advantages and enhanced performance of IL-based ABS [2], no attempt
have been made to use pH as a switch to change between two-phase and homogeneous regimes.
The major goal of this work is to understand and exploit switchable IL-based ABS triggered by pH.
In the first part of this study, a large array of ABS at different pH values was obtained by
combination of potassium citrate with different Ils in aqueous solution. The reversibility of the
IL-based ABS was then ascertained by addition of citric acid or potassium hydroxide, i.e., by
manipulation of the speciation of the organic salt used. In addition to IL-salt mixtures,
polymer-IL-based ABS were also explored inducing the switchable behaviour through the IL anion
speciation. Finally, these ABS were used for the selective separation of organic and inorganic dyes
as shown in Figure 1.
!"#$&
!"#$%
Figure 1: Selective separation of sudan III and pigment blue 27.
Acknowledgements: This work was financed by national funding from Fundao para a Cincia e a (FCT) through the
projects PTDC/QUI-QUI/121520/2010and PEst-C/CTM/LA0011/2013. A. M. Ferreira acknowledges FCT for the PhD
grant SFRH/BD/92200/2013. M. G. Freire acknowledges the European Research Council (ERC) for the Starting Grant
ERC-2013-StG-337753.
References
[1] Y. Kohno, H. Ohno, Chem. Commun.,2012, 48: 7119-7130.
[2] M. G. Freire, A. F. M. Cludio, J. M. M. Arajo, J. A. P. Coutinho, I. M. Marrucho, J. N. Canongia Lopes and L. P.
N. Rebelo, Chem. Soc. Rev., 2012, 53: 140-143.
K1
Ionic Liquids in the Biorefinery

Agnieszka Brandta, Jason P. Halletta, Tom Weltonb,*
a
Department of Chemical Engineering, Imperial College London, UK

b
Department of Chemistry, Imperial College London, UK
*t.welton@imperial.ac.uk
As a new chemicals industry based upon biomass sources emerges, there is an opportunity to create
this on a sustainable basis from the outset. Ionic liquids have already shown their use in creating a
more sustainable chemicals industry through the introduction of more sustainable processes. Using
the knowledge that we have gained about the effects of solvent-solute interactions in ionic liquids,
we have been developing these as solvents for lignocellulosic biomass processing.
Most approaches to the processing of biomass with ionic liquids have focused on the dissolution of
cellulose. However, these potential processes have a number of drawbacks, greatest among these
being their intolerance to water.
We present here our development of ionic liquids to fractionate lignocellulosic biomass
delignification, so that cellulose is made available for subsequent biological processing and
lignin component can be recovered for conversion into high value chemicals. We consider
optimum conditions for these reactions. We also present the use of ionic liquids to reduce
energy requirements of mechanical processing of the biomass.
K2
via
the
the
the
Phosphonium Alkyl-PEG Sulfate Ionic Liquids as a Novel Activating Agents for

Lipase
Yui Matsubara,a Hiroyuki Harami,aYukinobu Fukaya,a,b Toshiki Nokami,a,b Toshiyuki Itoha,b*
a
Department of Chemistry and Biotechnology, Graduate School of Engineering, Tottori University,

Center for Research on Green Sustainable Chemistry, Tottori University, 4-101 Koyama-minami, Tottori
680-8552,Japan
*titoh@chem.tottori-u.ac.jp
Lipases are the most widely used enzymes applicable for organic synthesis. We have been
investigating the use of ILs in asymmetric lipase-catalyzed reactions, and have developed
methodologies for a recyclable use system of
lipase in an ionic liquid reaction medium [1].
OH
+ acyl donor
L
We then established a powerful means of
2
1
R
+PL1-PS (enzyme)
R
activating lipase protein by coating it with
+ Ionic Liquid ([P444MP][Tf2N]
()-1
1-butyl-2,3-dimethylimidazolium alkyl PEG
sulfate ionic liquid: the ionic liquid coated
Burkholderia cepacia lipase (Lipase PS)
displayed excellent reactivity for many
()-1
substrates in conventional organic solvents
+ acyl donor
Products
[2,3]
.
OAc
Here we report the results of development of
the second generation IL type coating
R1 R2
stirring
(R)-2
material for lipase activation: we found that
1 torr 15
at 35C
OH
(methoxyethoxymethyl)tributylphosphonium
min. at rt
+ hexane/
1
PEG
sulfate
([P444MEM][cetyl
R2
R
ether
(S)-1
(OCH2CH2)10SO4](PL1) worked as an
excellent activating agent of lipase PS. In
particular, a remarkable acceleration of
organic layer
enantioselective acyaltion took place when
the reaction was carried out in a
IL layer (enzyme)
phosphonium IL, such as [P444MP][Tf2N] as a
solvent
with
maintaining
perfect
Bu
O
n-C16H33 O
enantioselectivity. Using the sytem, we
P
S O
O
Bu
R
10
succeeded in demonstrating recyclable use
O
Bu
of the catalyst without any loss of reactivity
PL1 (R= CH2OCH2CH2OMe)
(Figure 1).
Figure 1. PL1-PS-coated Lipase PS-catalyzed
enantioselective acylation in an IL solvent system.
References
[1] Itoh, T.; Akasaki, E.; Kudo, K.; Shirakami, S. Chem. Lett. 2001, 31, 262-263.
[2] Itoh, T.; Matsushita, Y.; Abe, Y.; Han, S-H.; Wada, S.; Hayase, S.; Kawatsura, M.; Takai, S.; Morimoto, M.; Hirose,
Y. Chem. Eur. J. 2006, 12, 9228-9237.
[3] A recent example, see: Abe, Y.; Yagi, Y.; Hayase, S.; Kawatsura, M.; Itoh, T. Ind. Eng. Chem. Res., 2012,
51, 9952-9958.
K3
Investigation on imidazolium ionic liquids and water molecules by matrix

isolation infrared spectroscopy
Doseok Kim* and Woongmo Sung
Department of Physics, Sogang University, Seoul 121-742, Korea
*doseok@sogang.ac.kr
We applied matrix isolation method[1] to observe absorption spectra of ionic liquids and
accompanying water molecules which are dispersed homogeneously in the medium of CCl4 as
monomers. 1M aqueous solutions of [BMIM]Cl and [BMIM]I were loaded on top of CCl4 liquid to
slowly let the ionic liquids and water molecules into the CCl4 matrix, and then FT-IR spectra were
taken through CCl4 phase as time elapses. As compared to the spectrum of pure water in CCl4
phase, new band was observed at 3421 cm-1 for [BMIM]Cl, and at 3452 cm-1 for [BMIM]I. In both
cases, absorption from bands corresponding to C(2)-H and C(4,5)-H stretch modes in imidazolium
cation was reduced almost to baseline level in comparison to bulk ILs spectra indicating that (1) the
[BMIM] cation exists in CCl4 without anion, and (2) hydrogen bonding between anion and cation
increases dipole strength of CH moieties in the imidazolium ring. Interestingly, amount of
transfered [BMIM]I and water to CCl4 phase is much larger than that in case of [BMIM]Cl. For this,
we propose that this difference in transport rate originates from excess ILs at the interface between
hydrophlic (aqueous solution) and hydrophobic (CCl4) medium increasing with the anion size.
Figure 1. FT-IR spectra of 1M [BMIM]Cl (left) and 1M [BMIM]I (right) transfered to CCl4
phase by using matrix isolation method. Inset is magnified spectra in the range of 3300 cm-1
to 3500 cm -1.
References
[1] Shultz M J, Vu T H, Meyer B, Bisson P, Acc. Chem. Res. 2012, 45: 15-22.
K4
Properties of ionic liquids and their applications in green chemistry

Buxing Han*
Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
*hambx@iccas.ac.cn
Ionic liquids (ILs) have received much interest due to their special properties such as negligible
vapor pressures, good thermal stability, high conductivity, wide electrochemical windows, and
strong solvent power for both organic and inorganic substances. In recent years, we carried out a
series of researches on the chemical thermodynamics of green solvents systems and their
applications in green chemistry, including mainly: 1)phase behavior and intermolecular molecular
interaction in ILs, supercritical (SC) CO2/IL systems; 2)chemical reactions and material synthesis
in SC CO2, ILs and CO2/ILs systems, special attention is paid to how the unusual properties of
green solvents affect chemical retractions material synthesis. In this presentation, we will discuss
our recent work related with ILs [1-11].
References
[1] X. C. kang, J. L. Zhang, B. X. Han, et al. J. Am. Chem. Soc., 2014, 136:3768-3771.
[2] Peng Li, J. L Zhang, Z. M. Xue, B. X. Han, et al., Nat. Commun., Accepted.
[3] P. Zhang, T. B. Wu, B. X. Han, Adv. Mater.,in press.
[4] H. L. Fan, Y. Y. Yang, B. X. Han, et al., Green Chem., 2014, 16:600-604.
[5] W. J. Lu, J. Ma, B. X. Han, et al., Green Chem., 2014, 16:221-225.
[6] J. L. Zhang, B. X. Han, Acc. Chem. Res., 2013, 46:425-433.
[7] L. Peng, J. L. Zhang, B. X. Han, et al., Angew. Chem. Int. Ed., 2013, 52:1792-1795.
[8]M. Y. He, Y. H. Sun, B. X. Han, Angew. Chem. Int. Ed., 2013, 52:9620-9633.
[9] Z. M. Xue, J. L. Zhang, B. X. Han, et al., Angew. Chem. Int. Ed., 2012, 51:12325-12329.
[10] Y. J. Zhao, J. L. Zhang, B. X. Han, et al., Angew. Chem. Int. Ed., 2011, 50:636-639.
[11] J. L. Zhang, B. X. Han, et al., Angew. Chem. Int. Ed., 2011, 50:9911-9915.
K5
Advances and directions in computational chemistry methods for ionic liquids

Ekaterina I Izgorodina*, Jason Rigby, Santiago Barrera Acevedo, Samuel Tan and Su Chen
School of Chemistry, Monash University, Wellington Rd, Clayton, VIC 3800
*katya.pas@monash.edu
Ionic liquids represent a fascinating class of materials due to a vast combination of cations and
anions. Over 1019 combinations could be potentially synthesized, each of those exhibiting different
physical properties. It has been shown that electronic structure properties of cations and anions
themselves such as hydrogen bonding ability, charge delocalisation, polarisability and many others
could affect resulting properties of a particular cation-anion combination in an unexpected way,
thus making it generally hard to predict properties of ionic liquids by solely looking at the chemical
structure of ions. As a result, there is a strong motivation in the field of ionic liquids to establish a
computer-aided design of ionic liquids with a view of the accurate prediction of their physical
properties such as melting points and transport properties prior to synthesis.
In this talk significant achievements in studying thermodynamics and transport properties of ionic
liquids from first principles methods as well as molecular dynamics simulations will be discussed.[1]
In particular, current advances in computational (quantum) chemistry methods developed in our
Monash Computational Chemistry group will be highlighted. More detail will be given to the
following topics: 1) importance of dispersion forces in ionic liquids and correlations of the
dispersion component of interaction energy with melting point[2,3] and 2) successful applications of
the Fragment Molecular Orbital (FMO) approach for studying structure and energetics of large
clusters of ionic liquids.[4,5]
Directions for future research in computational chemistry methods will be identified, with emphasis
on the development of 1) a robust spin-component scaled second-order perturbation theory method
(MP2) for large-scale calculations of ionic liquids and 2) novel force fields for more accurate
molecular dynamic simulations of future ionic liquids.
References
[1] Izgorodina EI, Phys. Chem. Chem. Phys., 2011, 13:4189-4207
[2] Izgorodina EI, Golze D, Maganti R, Armel V, Taige M, Schubert TJ, MacFarlane DR, Phys. Chem. Chem. Phys.,
2014, 16:7209-7221
[3] Bernard UR, Izgorodina EI, MacFarlane DR, J. Phys. Chem. C, 2010, 114:2047220478
[4] Izgorodina EI, Rigby J, MacFarlane DR, Chem. Commun., 2012, 48:1493-1495
[5] Chesman ASR, Hodgson JL, Izgorodina EI, Urbatsch A, Turner DR, Deacon GB, Batten SR, Cryst. Growth. Des.,
2014, 14:19221932
K6
Solvent Nanostructure, the Solvophobic Effect and Amphiphile Self-Assembly in

Ionic Liquids
Tamar. L. Greaves and Calum J. Drummond
School of Applied Sciences, RMIT University, GPO Box 2476, Melbourne VIC 3001 Australia
tamar.greaves@rmit.edu.au
calum.drummond@rmit.edu.au
Abstract
The ability of ionic liquids (ILs) to support amphiphile self-assembly into a range of mesophase
structures has been established as a widespread phenomenon. From the ILs evaluated as
self-assembly media, the vast majority have supported some lyotropic liquid crystal phase
formation. Many neat ionic liquids have been shown to segregate into polar and non-polar domains
to form a nanostructured liquid. A very strong correlation between the nanostructure of the ionic
liquid and its characteristics as an amphiphile self-assembly solvent has been found. In this
presentation, we discuss ionic liquids as amphiphile self-assembly media, and identify trends that
can be used to distinguish which ionic liquids are likely to have good promotion properties as
self-assembly media. In particular these trends focus on the nanostructure of neat ionic liquids, their
solvent cohesive energy density, and the related solvophobic effect. We forecast that many more
ILs will be identified as amphiphile self-assembly solvents in the future.
K7
Solvation and Structure in Protic Ionic Liquids and Their Solutions

Gregory Warr,a* Stephen A. Bernard,a Rob Atkin,b Robert Hayes,b and Silvia Imbertic
a
The University of Sydney, Sydney, Australia

The University of Newcastle, Newcastle, Australia
c
STFC, Rutherford Appleton Laboratory, Didcot, UK Australia
*gregory.warr@sydney.edu.au
b
The bulk structure of a range of primary ammonium protic ionic liquids (PILs) and their solutions is
described using multiple isotopic substitution neutron diffraction analysed by empirical potential
structure refinement. This approach gives an extremely detailed picture of liquid structure, and
particularly of the atomic arrangements around hydrogen atoms.[1] By varying the anion type
(nitrate, formate, hydrogensulfate and thiocyanate), the length of the alkylammonium chain from
ethyl to butyl, and by comparing these with ethanolammonium PILs, we show how the long-range
amphiphilic nanostructure in the liquid arises from local electrostatic interactions and H-bonding
geometries.[2] The structures formed are interpreted in terms of a simple geometrical packing model,
using concepts borrowed from surfactant self-assembly.
The origins of amphiphilicity[3] and the resultant long range nanostructure in these PILs is also
explored by examining mixtures formed from amphiphilic (alkyl-chained) and non-amphiphilic
ethanolammonium salts, as well as that in solutions of water[4] and various salts dissolved in both
classes of PILs. Solutes that dissolve exclusively into polar domains of PILs are found to modify
H-bonding and affect amphiphilic nanostructure, as well as changing the packing geometry and the
domain structure.
References
[1] The Nature of Hydrogen Bonding in Protic Ionic Liquids R. Hayes, S. Imberti, G.G. Warr, R. Atkin, Angew.
Chemie Intl Ed. 2013, 52, 4623-4627
[2] "Effect of cation alkyl chain length and anion type on protic ionic liquid nanostructure"
R. Hayes, S. Imberti, G.G. Warr, R. Atkin, submitted to J. Phys. Chem C 2014
[3] Surface Composition of Mixtures of Ethylammonium Nitrate, Ethanolammonium Nitrate and Water D. Wakeham,
D. Eschebach G.B. Webber, R. Atkin, G.G. Warr, Aust. J. Chem. 2012, 65, 1554-1556.
[4] How Water Dissolves in an Ionic Liquid R. Hayes, S.Imberti, G.G. Warr, R. Atkin, Angewandte Chemie Intl Ed.
2012 51, 74687471
K8
Ionic liquids-based catalysts for carbon dioxide conversion

Liang-Nian He*, Zhen-Zhen Yang, An-Hua Liu, Jian Gao
State Key Laboratory and Institute of Elemento-Organic Chemistry, Nankai University, Tianjin, 300071, P. R. China
* heln@nankai.edu.cn
Upgrading use of carbon dioxide from waste into high valuable chemicals, materials, particularly to
fuel-related products has attracted much interest from a standpoint of green chemistry and
sustainable development, since CO2 can be regarded as a ubiquitous, abundant, cheap, and nontoxic
C1 feedstock in organic synthesis.[1-4] To be delighted, several chemicals such as carbonates, urea,
salicylic acid and methanol have been produced from CO2 on an industrial scale. However, the
reactions involving CO2 are commonly carried out at high pressure due to inherent thermodynamic
stability and kinetic inertness, which may not be economically suitable and also pose safety
concerns. The challenge is to develop efficient catalysts that are capable of activating CO2 under
low pressure (preferably at 1 atm), and thus incorporating CO2 into organic molecules
catalytically[5]. Accordingly, only if we understand the underlying principles of CO2 activation, can
the goal of using CO2 as an environmentally friendly and economically feasible source of carbon be
achieved. In other words, transformation of CO2 will inevitably rely on its activation by diverse
catalytic systems including metal complexes and organic catalysts e.g. functionalized ionic
liquids,[4] frustrated Lewis pairs.
We believe that a partial results on CO2 chemistry[3] disclosed herein will stimulate further interest
in scientific exploration that may lead to the development of CO2 as a sustainable carbon/oxygen
source for a wide set of value-added fine/bulk chemicals, pharmaceuticals, polymers fuels in carbon
neutral manner.
References
[1] a) Aresta M, Dibenedetto A, Angelini A. Chem Rev, 2014, 114: 1709; b) L.-N. He, et al., Carbon dioxide chemistry
(in Chinese), Chinese Science Press, Beijing, 2013.
[2] a) He M, Sun Y, Han B. Angew. Chem. Int. Ed., 2013, 52, 9620; b) Yang Z Z, He L N. Energy Environ. Sci., 2012,
5: 6602; c) Boot-Harndford W E, Fennell, P S. Energy Environ. Sci., 2014, 7: 130.
[3] a) Yang Z-Z, He L-N, Energy Environ. Sci., 2011, 4: 3971; b) Liu A-H, Yu A, He L-N. Angew. Chem. Int. Ed.,
2012, 51: 11306; c) Song Q W, He L N. Green Chem., 2014, 16: 1633.
[4] MacFarlane D R, Watanabe M. Energy Environ. Sci., 2014, 7: 232. Zhang S, He L N. ChemSusChem, 2014, 7, DOI:
10.1002/cssc.201400133.
K9
Interfacial reactions of the ionic liquid 1-octyl-3-methyl-imidazolium

bis(trifluoromethylsulfonyl)amide
Frank Endres*
Institute of Electrochemistry, TU Clausthal, 38678 Clausthal-Zellerfeld, Germany
*frank.endres@tu-clausthal.de
Ionic liquids have attracted the interest of electrochemists as they are versatile, with wide
electrochemical windows and low vapor pressures. Consequently, elements and compounds can be
made, that cannot be obtained by aqueous electrochemistry like e.g. Si, Ge, SiGe, Al, Ta and others.
Furthermore, the low vapor pressure and the wide thermal windows allow investigations under the
condition of an ultrahigh vacuum (UHV) and at elevated temperatures, respectively.
In the recent years the interfacial behavior of ionic liquids has attracted considerable attention, as
they are remarkably strongly adsorbed on electrode surfaces. They form several layers that can be
probed by Atomic Force Microscopy (AFM), and the adsorption is dependent on the electrode
potential: the more negative/positive from the open circuit potential the electrode potential is, the
more strongly the liquids are usually adsorbed. Impurities like LiCl seem to break these layers to a
certain extent, which might explain why the deposition of Nb and Ta is much easier in the presence
of Li-salts.
We have investigated the interfacial behavior of [OMIm]TFSA by electrochemistry, in situ
Scanning Tunneling Microscopy (STM) and UHV STM/AFM. On highly oriented pyrolytic
graphite (HOPG) it is quite challenging to probe the lattice of HOPG with atomic resolution. Under
electrochemical conditions several superstructures form close to the cathodic decomposition
potential of the cation and UHV AFM of ultrathin layers shows the formation of layers as well.
Ionic liquids are also discussed as electrolytes for lithium ion batteries, as they are supposed to be
chemically quite stable. However, if [OMIm]TFSA is evaporated on a thin Li film or vice versa
both the cation and the anion get attacked by Li, leading to several decomposition products.
Interestingly, even Li2O leads to a certain degradation of the IL.
References
[1] Timo Carstens, Ren Gustus, Oliver Hfft, Natalia Borisenko, Frank Endres, Hua Li, Ross J. Wood, Alister Page,
Rob Atkin, A combined STM, AFM and DFT study of the HOPG / 1-octyl-3-methyl-imidazolium
bis(trifluoromethylsulfonyl)amide ([OMIm]Tf2N) Interface, Journal of Physical Chemistry C, under review
[2] Mark Olschewski, Ren Gustus, Marcel Marschewski, Oliver Hfft, Frank Endres, Spectroscopic characterization
of
the interaction of lithium with thin films of the ionic liquid 1-Octyl-3-methylimidazolium
bis(trifluoromethylsulfonyl)amide, Physical Chemistry Chemical Physics, under review.
K10
Ionic liquids for controlled synthesis of functional materials for energy-related

applications
Sheng Daia,b
a
Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA
b
Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996, USA
*dais@ornl.gov
Conventional synthesis of functional materials relies heavily on water and organic solvents.
Alternatively, the synthesis of functional materials using, or in the presence of, ionic liquids
represents a burgeoning direction in materials chemistry.[1] Use of ionic liquids in solvent extraction
and organic catalysis has been extensively studied, but their use in materials synthesis has just
begun. Ionic liquids are a family of non-conventional molten salts that can act as both templates and
precursors to functional materials, as well as solvent. They offer many advantages, such as
negligible vapor pressures, wide liquidus ranges, good thermal stability, tunable solubility of both
organic and inorganic molecules, and much synthetic flexibility. The unique solvation environment
of these ionic liquids provides new reaction media for controlling formation of porous materials and
tailoring morphologies of advanced materials. Challenges and opportunities in this research area
will be discussed.
Acknowledgments: This work was conducted at the Oak Ridge National Laboratory and supported
by the Division of Chemical Sciences, Geosciences and Biosciences, Office of Basic Energy
Sciences, U.S. Department of Energy, under contract No. DE-AC05-00OR22725 with UT-Battelle,
LLC.
References
[1] Ma, Z.; Yu, J. H.; Dai, S., Adv. Mater. 2010, 22, 261-285.
K11
Bulk and Interfacial Nanostructure in Solvate Ionic Liquids

Rob Atkina,* Thomas Murphy,a Aaron Elbourne,a Hua Li,a Ben Mclean,a Ross Wood,a Kazuhide Ueno,b Alister Page,a
Greg Warrc Masayoshi Watanabe,b
a
b

Yokohama National University, Yokohama, Japan
c The University of Sydney, Sydney, Australia
*rob.atkin@newcastle.edu.au
Solvate ionic liquids (SILs) are formed by certain glyme Li salt complexes, prepared by mixing
equimolar mixtures of a glyme and a Li salt (e.g. LiNO3, LITFSA etc) under ambient conditions.
The Li ion is bound by the glyme to form a complex cation, with the anion coming from the lithium
salt. The resultant SIL has the form [Li(glyme)]X, and has physicochemical properties that are
typical of ionic liquids including high thermal stability, a wide potential window, high ionic
conductivity, and high Li+ transfer number.[1] The high concentration of lithium in SILs applications
makes them highly appealing for a wide range of applications including electrochemical devices
such as electric double-layer capacitors, fuel cells, dye-sensitized solar cells, and lithium ion
batteries (LIBs).[2] This presentation will describe the bulk nanostructure of solvate ionic liquids
determined using neutron diffraction data and empirical potential structure refinement fits. The
interfacial nanostructure of the solvate ionic liquids will be probed using the atomic force
microscope (AFM). AFM force curves show how the nanostructure of the liquids normal to
electrode interfaces varies as a function of potential, and lateral surface nanostructure is elucidated
using high resolution amplitude modulated atomic force microscope images. Experimental results
will be analysed in conjunction with quantum mechanical simulations.
References
[1] Tamura, T.; Yoshida, K.; Hachida, T.; Tsuchiya, M.; Nakamura, M.; Kazue, Y.; Tachikawa, N.; Dokko, K.;
Watanabe, M. Chemistry Letters 2010, 39, 753.
[2] Ueno, K.; Yoshida, K.; Tsuchiya, M.; Tachikawa, N.; Dokko, K.; Watanabe, M. The Journal of Physical Chemistry
B 2012, 116, 11323.
K12
Highly Selective Electrochemical Fluorination Using Recyclable Mediators in

Poly(hydrogen fluoride) Salt Ionic Liquids
Toshio Fuchigami,* Takajiro Sawamura, Kohta Takahashi, Shinsuke Inagi
Department of Electronic Chemistry, Tokyo Institute of Technology, Yokohama, Japan
Poly HF salt ionic liquids, which mainly consist of amine or ammoinium fluoride and HF, have
excellent conductivity because of their low viscosity. In order to establish a selective fluorination
process, we have systematically studied solvent-free electrochemical fluorination of organic
molecules[1] and conducting polymers[2] in poly HF salt ionic liquids. Electrochemical fluorination
very often causes anode passivation, which suppresses faradaic current and decreases product yield
and current efficiency.
In order to overcome such problem, we have developed recyclable
mediatory systems for electrochemical fluorination as follows.
1) Recyclable Task-Specific Ionic Liquid Mediators for Selective Fluorination:
Task-specific ionic liquids having iodoarene and triarylamine mediators were prepared and they
were successfully used as mediator for anodic fluorination and fluorodesulfurization in poly HF salt
ionic liquid.[3,4] Both the mediator and ionic liquid were recycled for the fluorination for many
-2e, 2F Iodobenzene
times.
with IL moiety
IF2
N
N
N
S
EWG
Et3N-3HF
EWG = COOEt, COMe, CN
F
S
EWG
without mediator: 0 - 39%

with mediator: 65 - 87%
2) Recyclable Polymer-Supported Mediator for Selective Fluorination:

We have achieved selective fluorination using recyclable polymer-supported iodoarene mediator.[5]
The polymer-supported mediator was readily separated and repeatedly used for the fluorination.
3) Recyclable Halogen Mediators for Selective Fluorination:
Electrolysis of various organic compounds using halogen mediators was also carried out in poly HF
salt ionic liquids to give the corresponding fluorinated products in excellent yields.[6] The recycle
use of the halogen mediator for the electrochemical fluorination was successfully demonstrated.
References
[1] Fuchigami T, Inagi S, Chem. Commun., 2011, 47:10211-10223.
[2] Inagi S, Hayashi T, Fuchigami T, Chem. Commun., 2009, 1718-1720.
[3] Sawamura T, Kuribayashi S, Inagi S, Fuchigami, Org. Lett., 2010, 12, 644-646.
[4] Takahashi K, Inagi S, Fuchigami T, Electrochim. Acta, 2012, 77, 47-53.
[5] Sawamura T, Inagi S, Fuchigami T, Adv. Synth. Catal., 2010, 352, 2752-2760.
[6] Takahashi K, Inagi S, Fuchigami T, J. Electrochem. Soc., 2013, 160, G3046-G3052.
K13
Pseudo-Encapsulation - Nano-Domains for Enhanced Reactivity in Ionic Liquids

Cameron C. Weber,a,b Anthony F. Masters, a Thomas Maschmeyer, a,*
a
School of Chemistry, The University of Sydney, Sydney, NSW 2006, Australia

Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139 USA
*thomas.maschmeyer@sydney.edu.au
An interesting question is whether or not ILs, when used as solvents, possess any unique
characteristics that may give rise to unusual reaction outcomes unattainable by neutral solvents of
comparable polarity. ILs, particularly those based on the imidazolium cation, have been shown to
possess significant structural heterogeneity resulting from the hydrophobic nature of the alkyl
side-chains when the side-chain is propyl or longer, leading to the formation of separate polar and
non-polar domains. These domains have been implicated in the use of ILs for separations and the
size-control of nanoparticles and polymers, however, their potential role in providing unique
reaction spaces that could lead to unprecedented precision in the control of organic reactions has not
been examined to date. Whether in chemical or biological systems, highly charged structured
nano-domains could play a significant and profound role across a vast range of reactions, akin to
transitory liquid zeolites.
Thus, to examine the effect of these domains on reactivity from a fundamental point of view, the
bimolecular nucleophilic substitution of N-(p-fluorophenyldiphenylmethyl)-4-picolinium chloride
([Ar3Pic][Cl]) has been chosen as a model reaction (Scheme 1). Previously, this system has been
shown to be sensitive to the solvation environment of the nucleophile, ROH, primarily due to the
similar charge of the electrophile in its initial and transition states, an effect that has also been found
for other N-tert-alkyl pyridinium systems.[1] As [Ar3Pic][Cl] is cationic in both initial and transition
states, it would be anticipated that the constituents of this salt would reside preferentially within the
polar domains of the IL. Through variation of the alkyl side-chains of the IL and the R group on the
hydroxylic substituting agent, any effects arising from interactions of the alcohol, ROH, with the
polar and non-polar domains can be delineated. To this end, the primary aliphatic alcohols
methanol, ethanol, 1-propanol, 1-butanol as well as water and benzyl alcohol have been examined
as nucleophiles.[2] From these experiments we were able to quantitatively delineate a
nanoencapsulation rate enhancing effect.
In conclusion, some general
remarks will be made
regarding the links between
of structural heterogeneity of
ionic liquids and ist effects in
material preparation and on
organic reactivity.[3]
S
c
h
e
m
e 1. General representation of the nucleophilic substitution of [Ar3Pic][Cl]. Reactions were
19
1
conducted at 294.3 K and monitored using F{ H} NMR
References
[1]
[2]
[3]
(a) Weber, C.C., Masters, A.F. & Maschmeyer, T., Journal of Physical Chemistry, B, 2012, 116(6):
1858 1864; (b) Organic & Biomolecular Chemistry, 2013, 11(15): 2534-2542.
Weber, C.C., Masters, A.F. & Maschmeyer, T., Angewandte Chemie, IEE, 2012, 51(46): 1148311486.
Weber, C.C., Masters, A.F. & Maschmeyer, T., Green Chemistry, 2013, 15(10): 26552679.
K14
Interaction and electrocatalytic conversion of CO2 with ionic liquids

Youquan Deng*
Centre for Green Chemistry and Catalysis, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences,
Lanzhou, 730000, China
*ydeng@licp.cas.cn
Functionalized Ionic liquids (ILs) could be promising for CO2 capture and conversion [1,2].
We have prepared a series of supported (such as glass powder without pores, SAPO-11 with mean
pore size ca. 1nm, and zeolitic imidazolate frameworks (ZIFs) with mean pore diameter 0.5 ~ 2.7
nm) ILs (such as EMImBF4, P4,4,4,6BF4, APMImBF4, P4,4,4PMBF4, EMImTriz, P4,4,4,6Triz), and they
were characterized with CO2-temperature programmed desorption (TPD), which has long been used
for characterization of heterogeneous catalyst, so as to investigate the possible interaction between
CO2 and ILs. The results showed that the temperatures at starting, maximum and completed
desorptions, possible different absorption sites, total desorption capacity, and even acidity or
basicity of the ILs could be revealed with TPD method. Supports have strong impact on the CO2
desorption behavior due to different pore sizes, structures and also probably due to
nano-confinement effect.
Electrochemical reduction of CO2 was studied in a series of ILs such as BMImBF4, BMImCl,
N4,4,4,4BF4, etc. aqueous solution as reaction medium on metal Ag cathode. It was found that metal
Ag catalyst cathode and BMImCl with 20 wt% H2O showed a excellent synergy in CO2 reduction
to CO with >99% of selectivity and with stable activity. The results suggested BMImCl played an
important role as electron acceptor from Ag to form electron-rich species which could activate CO2.
Also, we studied ZIF-Cu(Im)2 as catalyst for the electrochemical reduction of CO2 in a solution of
ILs + CH3CN + H2O. The results showed that electrocatalytic reduction of CO2 to CH4, CO and H2
(volume ratio: 3:6:1) in the solution containing BMImPF6 (80 wt%) + CH3CN (18 wt%) + H2O (2
wt%) saturated with CO2 was observed. Other possible products such as formic acid or methanol etc
in solution were not detectable. CH4 formation may be related to the synergy of specific IL and
micro-environment in of ZIF-Cu(Im)2 containing Cu and imidazolate species. Detailed results will
be presented.
References
[1] C. Wang, X. Luo, H. Luo, D. Jiang, H. Li, S. Dai, Angew. Chem. Int. Ed., 2011, 50: 4918-4922.
[2] Y. Oh and X. Hu, Chem. Soc. Rev., 2013, 42: 2253-2261.
This work was supported by National Natural Science Foundation of China (No. 21002107 and 21373247).
K15
Hydrogen Bonding Interactions within Choline-Chloride-Urea Mixtures

Patricia Hunt*
Imperial College London, United Kingdom
*p.hunt@imperial.ac.uk
When pure choline chloride (mp 302C) is combined with a H-bond donor such as urea (mp 133C)
in a ratio of 2:1 urea:[choline chloride] the freezing point of the resultant mixture is only 12C.[1]
Some depression of the melting/freezing point is expected based on ideal mixing of the pure
compounds, however a more substantial depression of the freezing point is thought to be due to the
changing nature of the intermolecular interactions within the liquid.
Deep eutectic solvents of this type, made from cheap readily available and biodegradable
chemicals, have potential for use in an increasing range of applications; materials synthesis,
dissolution, lubrication, electrochemistry and biomass pretreatment. However, there is not yet a
clear understanding of the intermolecular interactions that lead to deviation from ideal behavior.
Halo-aluminate eutectics are known to form new chemical species (for example AlCl3
becomes [AlCl4]) where the Cl has become "complexed". In analogy, the Cl of choline chloride
(ChCl) can form complexes with urea (for example [urea-Cl-urea]). While the new species formed
is not covalent in nature, it is thought that H-bonding interactions play a critical role. The anionic
charge can now be distributed over a larger molecular species reducing the cation anion association
strength and lowering the melting point. Nevertheless, it is also possible for urea to interact with a
choline cation ([urea-Ch]+) or additional urea molecules (urea-urea).
We have employed ab-initio quantum chemical methods (B3LYP-D/6-311++G(d,p)) to
study the molecular association and H-bonding within this system. The component ions and urea
molecules have been combined in pairs and the unencumbered H-bonds evaluated. Clusters
containing 1, 2 or 3 urea molecules for each ion or ion-pair have been examined. The extent and
range of H-bonding has been studied using energetic, structural, electronic (NBO, ESP and AIM
analysis) and orbital (MO) descriptors. Within the clusters we observe a subtle interplay between
electrostatics and the different types of hydrogen bond that can form. The aim has been to address a
number of questions: Is the [Cl(urea)2] motif particularly stable? Has the charge become
delocalised? How strong are the H-bonds? What structures do the Ch-Cl-urea2 clusters take on?
Can this information be used to help rationalise selected properties of the choline chloride urea
mixture?
Clusters of Choline-Chloride and Urea.
References
[1] A. P. Abbott, G. Capper, D. L. Davies, R. K. Rasheed and V. Tambyrajah, Chem. Comm., 2003, p70.
K16
Reactivity of Carbon Dioxide or Sulfur Dioxide with small anionic donors in

ionic media
Jason A.C. Clyburne, a* Luke J. Murphya, Katherine N. Robertsona, Ulrike Werner-Zwanzigerb, Jani Moilanenc, and
Heikki M. Tuononenc
a
!The Atlantic Centre for Green Chemistry, Department of Chemistry, Saint Marys University, Halifax, Nova Scotia,
B3H 3C3, Canada. Tel: 01 902 420 5827.
!Department of Chemistry and Institute for Research in Materials, Dalhousie University, Halifax, Nova Scotia, B3H
c
4J3, Canada.
Department of Chemistry, P.O Box 35, FI-40014, University of Jyvskyl, Finland. Tel: 358 45 235 8588.
* jason.clyburne@smu.ca
It has long been postulated that cyanoformate, [NCCO2]-, forms and then rapidly decomposes to
CO2 and CN- during the 1-aminocyclopropane-1-carboxylic acid oxidase -catalyzed biosynthesis of
ethylene. We have now isolated and fully characterised this elusive and reactive anion as its
tetraphenylphosphonium salt. The free cyanoformate anion is calculated to be thermodynamically
stable only in low dielectric media due to its very weak C-C bond. Solution stability studies have
substantiated this result while hydrolysis has proven to yield the bicarbonate salt, an important
participant in the ACCO reaction. We suggest that under favourable conditions the cyanoformate
anion is longer lived than previously thought and shuttles potentially toxic cyanide away from the
active site ofthe enzyme, suggesting a subtle role for CO2 as a protecting group in a biological
setting. Other adducts of small anions with acidic gases will also be described, including
crystallographic studies and in situ spectroscopic studies of the dissolved gaseous reagents in, for
example, ionic liquids.
K17
Ionic Liquid-Polymer Composite Films for Energy Applications

Linpo Yu, Alasdair Taylor, George Z. Chen*
Department of Chemical and Environmental Engineering, and Energy and Sustainability Research Division, Faculty of
Engineering, University of Nottingham, University Park, Nottingham, NG7 2RD, UK
*george.chen@nottingham.ac.uk
Ionic liquids possess some unique and desirable physicochemical properties for energy applications,
notably low volatility and wide electrochemical window. However, their incorporation in many
energy related processes and devices is not always straightforward because liquids often do not
comply with manufacturing and application needs. A good example of energy application of ionic
liquids is in smart windows that can modulate light transmission into a built environment in
response to the temperature change, and hence save energy consumption for air-conditioning. The
low volatility of ionic liquids can be utilised to accommodate thermochromic reactions in prolonged
heating and cooling cycles, but such liquids must be first made into transparent films for attachment
onto windows.[1] Another energy application example of ionic liquids is in supercapacitors. These
new electrochemical energy storage devices are featured by their high power density and long
charging-discharging cycle life in comparison with rechargeable batteries, including those of
lithium ion types. However, supercapacitors with a conventional aqueous or organic electrolyte
suffer from very low energy density. The wide electrochemical window of ionic liquids is very
much needed for development of high energy
density supercapacitors in which the energy a
b
capacity is proportional to the square of the
voltage.[2] One of the key technical issues for
using an ionic liquid as the electrolyte in
supercapacitors is how to incorporate the liquid
into the separator membrane. In this presentation,
several laboratory approaches to making ionic
liquid polymer composite membranes as Figure 1. (a) Photograph of a membrane of
exemplified in Figure 1, and the preliminary ionic liquid-PVDF composite prepared by a
results from testing these membranes for solvent-free method, and (b) SEM image of
thermochemical and electrochemical applications the surface of the composite membrane.
will be reported.
References
[1] Wei XJ, Yu LP, Jin XB, Wang DH, Chen GZ, Adv. Mater., 2009, 21, 786-780.
[2] Liu CG, Yu ZN, Neff D, Zhamu A, Jang BZ, Nano Lett., 2010, 10, 4863-4868.
Acknowledgement: This work was partly supported by E.ON AG 2007 International Research
Award - Energy Storage, University of Nottingham Hermes Fellowship and Season Long Cleantech
Ltd (Beijing). Responsibility for the content of this presentation lies with the authors.
K18
Parallel Lectures A
Ionic liquids in Lithium, Sodium, Magnesium and Zinc batteries tailoring

composition and performance
Patrick Howletta, Maria Forsytha and Douglas MacFarlaneb
a
b
Australian Centre of Excellence for Electromaterial Science and Institute for Frontier Materials, Deakin University,
Burwood Highway, Burwood Victoria Australia 3125
Australian Centre of Excellence for Electromaterial Science and School of Chemistry, Monash University, Wellington
Rd., Clayton Victoria Australia 3800.
*Corresponding authors e-mail address: patrick.howlett@deakin.edu.au
The electrolyte is one of the key components of an energy storage device required to achieve, for
example, high reliability and safety as well as high energy density. There are numerous battery
chemistries possible, although lithium-ion has become one of the most common technologies for
portable electronics and is making its way increasingly into electric vehicles and stationary storage.
Other technologies that continue to be investigated include Sodium, Zinc and Magnesium based
systems.
We have found that pyrrolidinium and phosphonium ionic liquids based on TFSI and FSI give
excellent performance for lithium batteries, particularly for electrolytes containing higher lithium
salt concentrations. The dicyanamide cation (dca) also gives good performance in lithium metal
devices, especially in the presence of small amounts of water. Our recent work has indicated that
these ionic liquids are also good candidates for reversible Na cycling, although the dca based
electrolytes are more sensitive to water in this case. On the other hand, for reversible Zn devices,
an electrolyte based on methyl, propyl pyrrolidinium (C3mpyr) dca with Zn(dca)2 and 3 wt% water
shows superior performance whilst the TFSI based ionic liquids do not support high current
densities nor high efficiency in plating and stripping of Zn.
Secondary Mg batteries remain elusive at present, however, we have shown that an electrolyte
based on a phosphonium chloride (P6,6,6,14 Cl) with addition of either water or ethylene glycol, leads
to steady discharge of a magnesium-O2 device with current densities up to 1mA/cm2 and a cell
voltage of 1.6V. An equivalent electrolyte based on dca did not support stable battery operation,
apparently due to the resistive interfacial layer that deposits on the Mg anode. In any metal air
device, the oxygen reduction reaction is also an important issue and this has also been shown to be
dependent on the nature of the ionic liquid.
A1
Investigation of the Ionic Conductivity Mechanism in Organic Ionic Plastic

Crystal Electrolytes
Usman Ali Ranaa*, R. Vijayaraghavanb, Cara M. Dohertyc, Amreesh Chandrad, Jim Efthimiadise, Anita J. Hillc, D. R.
MacFarlaneb and Maria Forsythe
a
Sustainable Energy Technologies (SET) center, College of Engineering, King Saud University, PO Box: 800, Riyadh
11421, Kingdom of Saudi Arabia
b
School of Chemistry and the ARC Centre of Excellence for Electromaterials Science, Monash University, Clayton, Vic,
3800, Australia
c
CSIRO Materials Science and Engineering & CSIRO Process Science and Engineering, Clayton South, Vic, 3169,
Australia
d
Department of Physics and Meteorology, IIT Campus, Kharagpur 721302, India
e
Institute for Frontier Materials and the ARC Centre of Excellence for Electromaterials Science, Deakin University, VIC
3125, Australia
*Corresponding authors e-mail address: urana@ksu.edu.sa
Abstract: Apart from many similar properties shared between Organic ionic Plastic Crystals
(OIPCs) and Ionic Liquids (ILs), one of the superior features of OIPCs is their high ionic
conductivities in the solid state that enable these soft, plastic like materials to address the challenges
(such as leakage and dependence on polymeric support) associated with the liquid electrolytes[1].
However, it is very important to understand the fundamental mechanism of ionic conduction in
these advanced materials in order to design the OIPCs for target applications. Here, we present a
detailed investigation of the ionic conductivity mechanism in the solid state plastic crystal phases of
Choline Triflate ([Ch][Tf]) and its acid containing compositions. The results from the conductivity
measurements revealed low activation energies (Ea ~ 16!17 kJ mol!1) in the high temperature
phases (Phases II and I) with Arrhenius behaviour evident for all samples suggesting a single,
thermally-activated ionic transport mechanism. The significantly low Ea values are consistent with
the observations of plastic crystal phases in these materials. Moreover, the thermally generated
defects (examined by Positron Annihilation Lifetime Spectroscopy (PALS) studies) in these plastic
crystal phases are also deemed to play a major role in the high ionic conductivity of these materials.
The structural characterization carried out by high-resolution powder XRD studies (examined at
Synchrotron beam line) showed a structural transformation from monoclinic ! cubic at the II!I
phase transformation in all samples. Finally, the cyclic voltammetry studies showed high proton
reduction currents in acid containing [Ch][Tf] compositions that were not observed for the neat
material, suggesting the avenue of proton conductivity in the acid containing plastic crystal systems.
The combination of temperature dependent high resolution XRD, PALS and multinuclear solid state
NMR techniques suggest a thermally activated, defect assisted conductivity mechanism of ionic
transport in these materials.
References
[1] J. M. Pringle, P. C. Howlett, D. R. MacFarlane and M. Forsyth, J. Mater. Chem., 2010, 20,
2056-2062.
A2
Ionic Liquids Based Vibration Energy Harvester

Weijie Konga,b, Xiaodong Hea,b, Shiguo Zhanga, Xiaoping Zhanga,* Youquan Dengb,*
a
School of Information Science and Engineering, Lanzhou University, Lanzhou 730000, China
Centre for Green Chemistry and Catalysis, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences,
Lanzhou 730000, China
*zxp@lzu.edu.cn; ydeng@licp.cas.cn
Energy harvesting from ambient vibration energy has attracted great attentions. Recently, a new
method for electrical power generation by mechanically modulating the electrical double layers
formed on the overlap areas between water bridge and conductive plates was proposed [1]. However,
water used for liquid media suffers from serious problems such as evaporation and poor
thermostability, which leads to sharply drop of output power.
Fig. (a) Schematic diagram of the ionic liquids based vibration energy harvester. (b) The output voltage waveform and corresponding
vibration waveform. (c) The output effective power versus vibration frequency for different ionic liquids.
Here, the ionic liquids (ILs) based vibration energy harvester (VEH) is presented (Fig. a), and the
electrical power is generated through periodically squeezing the ILs bridge (Fig. b). Using ILs as
liquid media, the VEH can work well in natural condition without needing of airtight space and in
the wide operating temperature range (up to 100 C). The influences of ILs type, operating
temperature, vibration frequency on power generation are studied. The results indicate that the
physicochemical properties of ILs importantly affect the performance of the VEH, and the
imidazolium ILs with short alkyl chain and low viscosity can generate more power (Fig. c).
Moreover, the output power of ILs based VEH rising with increasing the operating temperature and
the output power at 100 C reaches to about 22 times of that at 15 C for EMImBF4. Additionally,
the output power increases at first, reaches the maximum and then may decrease with frequency. A
prototype of the ILs based VEH demonstrated the maximum power density of 0.12 mW/m2 at room
temperature and 0.70 mW/m2 at 100 C.
In order to enhance output power, the hydrophobic dielectric in VEH can be replaced by electret
which retains charges for a long time. The maximum power density could reach 11.93 mW/m2 at
room temperature. Compared with the original ILs based VEH, the output power has been
improved as much as 99 times. Further works for increasing output power, such as rational design
and synthesis of ILs, optimizing the fabrication of VEH, are under investigation.
References
[1] J. K. Moon, J. Jeong, D. Lee, H. K. Pak, Nat. Commun., 2013, 4: 1487.
This work is supported by the National Natural Science Foundation of China (No. 21373247, 21103208).
A3
Electroactive ionic liquids as functional electrolytes for energy storage devices

Dominic Rocheforta*, Bruno Glinasa, Han Jin Xiea, Soumia El Khakania, Dean McNeilb
a
Dpartement de chimie, Universit de Montral, Montral, Canada

Energy, Mining and Environment, National Research Council Canada, Ottawa, Canada
*dominic.rochefort@umontreal.ca
The chemical modification of an ionic liquids component with a redox group results in a phase
with very high concentrations in electroactive centres with unique electrochemical properties. It
allows electrochemistry reactions to be carried out directly on the solvent with reversible
reactions at moderate and selectable potentials, in opposition to electrochemistry done on pure
traditional molecular solvents where the reactions with the liquid phase are irreversible. The
modification of imidazolium with a ferrocenyl group for instance was studied by Murray et al., who
showed a contribution of electron hopping between redox centres to the charge transport properties
in the ionic liquid.[1,2]
Our research focuses on the development of new electroactive ionic liquid that can be applied in the
electrolyte of energy storage devices, either in their pure form or in mixture with conventional
solvents.[3,4] In this contribution, the development of new electroactive ionic liquids and their use to
modify the electrolyte of lithium-ion batteries and supercapacitors is discussed. The structures of
these ionic liquids, modified by the addition of either an organic redox group on imidazolium or a
ferrocenyl on the TFSI anion, are presented in Figure 1.
!
FcMIm-TFSI
E0 = 0.63 V vs. NHE
BMIM-FcTFSI
E0 = 0.78 V vs. NHE
MDTBIm-TFSI
E0 = 1.05 V vs. NHE
Figure 1. Electroactive ionic liquids based on imidazolium-TFSI.

The effect of the addition of an electron-rich moiety on the structure of the ionic liquids will be
firstly discussed. The major impact of this modification is an increase in the viscosity due to the
larger size of the ions and to the stronger intermolecular interactions associated with the !-bonding
ability of the redox centres added. The melting point is also significantly increased, reaching up to
94C in the case of MDTBIm-TFSI, but was found between 40 and 60 for various structures
modified with ferrocene. The discussion will next cover the electrochemical behaviour that was
studied for all electroactive ionic liquids in mixtures with typical solvent and for the pure phases of
the ferrocene-modified ILs. Finally, the incorporation of these ionic liquids in the electrolyte of
lithium-ion batteries will be presented as a mean to prevent cathode overcharging and increase their
safety.
References
[1] Balasubramanian R, Wang W, Murray RW, J. Am. Chem. Soc., 2006, 128: 9994-9995.
[2] Wang W, Balasubramanian R, Murray RW, J. Phys. Chem. C, 2008, 112: 18207-18216.
[3] Forgie JC, Rochefort D, RSC Adv., 2013, 3: 12035-12038.
[4] Forgie JC, El Khakani S, MacNeil DD, Rochefort D, Phys. Chem. Chem. Phys., 2013, 15: 7713-7721.
A4
Electroanalytical studies at solid-liquid and liquid-liquid interfaces

incorporating room temperature ionic liquid phases
Damien W. M. Arrigan,a,* Debbie S. Silvester,a Junqiao Lee,a Krishnan Murugappan,a Eva Alvarez de Eulate,a Julian D.
Gale.a
a
Nanochemistry Research Institute, Department of Chemistry, Curtin University, GPO Box U1987, Perth, Western
Australia 6845, Australia.
*Corresponding author, d.arrigan@curtin.edu.au
The properties of room temperature ionic liquids (RTILs), such as low volatility, intrinsic
conductivity, wide electrochemical windows, good solvating properties and tuneability, make them
interesting platforms for studies relating to analytical methods and sensor devices. We have thus
embarked on studies of the behaviour of RTILs with respect to analytical chemical detection.
The electrochemical behaviour of gases dissolved in RTILs has been examined at
screen-printed electrodes.[1] Voltammetric reduction of dissolved oxygen on Pt screen-printed
electrodes suggest a reaction of electrogenerated superoxide with the compounds that make up the
ink of these electrodes, although RTILs containing a pyrrolidinium cation provided a more
chemically stable solvent environment than those with imidazolium and phosphonium cations.[2]
The analytical utility of these reductions was examined on a range of screen-printed electrodes and
linear responses were observed between current and % concentration in the range 10100% O2.
Pre-treatment of the screen-printed surface was found to impact significnatly the electrode
performance.
The interface between two immiscible electrolyte solutions (ITIES) can be usefully
subjected to electrochemical polarisation and employed for detection of non-redoxactive substances
based on ion-transfer reactions rather than electron transfer. The electrochemical behaviour of the
interface between water (W) and a hydrophobic RTIL, trihexyltetradecylphosphonium
tris(pentafluoroethyl)trifluorophosphate ([P14,6,6,6][FAP]) was studied in micro-array format.[3]
Voltammetry was used to examine the behaviour of the microinterface array using a series of
simple ion transfer processes. In the presence of an acidic aqueous phase, interactions between FAPand protons were observed using cyclic voltammetry. Preliminary computations indicate that
proton-[FAP]- interaction leads to loss of HF. Furthermore, protein behaviour was studied at these
W|RTIL interfaces.[4] Electro-adsorptive accumulation of lysozyme at the interface enabled
detection at micromolar concentrations.
References
[1] K. Murugappan, J. Lee, D.S. Silvester, Electrochem. Commun., 2011, 13: 1435-.
[2] J. Lee, K. Murugappan, D.W.M. Arrigan, D.S. Silvester, Electrochim. Acta, 2013, 101: 158168.
[3] D.S. Silvester, D.W.M. Arrigan, Electrochem. Commun., 2011, 13: 477479.
[4] E. Alvarez de Eulate, D.S. Silvester, D.W.M. Arrigan, Chem. Asian J., 2012, 7: 2559-2561.
A5
Ionic Liquids for aluminum plating and LCA of the Electrolyte

Boyan Ilieva, Peter von Czarneckia, Maria Ahrensa, Thomas J. S. Schuberta
a
Iolitec Ionic Liquids Technologies, Heilbronn, Germany

*info@iolitec.de
The reduction of aluminum from organic solutions of Al-halides was shown by Plotnikov for the
first time in 1899.[1] Various investigations on electrolyte variations for Al plating were already
described, leading in some cases to galvanic depositions of purities beyond 99.999%.[2]
Nevertheless, self-ignition of the organo-Al compounds, the flammability of the organic electrolytes
as well as the high costs of the Al-source are still important challenges. In addition, other types of
Al-plating electrolytes have been developed, but always with drawbacks such as flammability, low
film purity, complicated process handling or high costs.
Ionic liquids (ILs) are ionic compounds with melting points below 100C, which have a range of
useful properties, among which non-flammability, thermal and chemical stability, very low vapor
pressure. Because of those in recent years, the focus was placed more and more on them as potential
electrolytes for the deposition of non-noble metals. Further some of them provide also a wide
electrochemical window, which is a important feature for the deposition.[3]
Current results of Al electroplating will be shown in our presentation (Figure 1). They have been
done at ambient temperature in different electrolytes, where the ionic liquid, the AlCl3
concentration and the additives are varied. So it was possible to deposit Al films of different
thickness on substrates with different shapes. Furthermore, a Life Cycle Assessment of the galvanic
Al-deposition by using IL is discussed.
Figure 1: Aluminum plated toy car

References
[1] V. A. Plotnikov, J. Russ. Phys. Chem. Soc, 1899, 31:1020.
[2] M. Glov, Surface Technology, 1980, 11: 357-369.
[3] Y. Zhao, T. J. VanderNoot, Electrochimica Acta, 1997, 42: 3-13.
A6
Multi-step Redox Control of C60-modified Au(111) Electrode in Ionic Liquids

Hiroyuki Uedaa, Katsuhiko Nishiyamaa,b, Soichiro Yoshimotob,c,*
a
Graduate School of Science and Technology, Kumamoto Univ., 2-39-1 Kurokami, Chuo-ku Kumamoto, Japan
Kumamoto Institute for Photo-Electro Organics (Phoenics), 3-11-38, Higashi-machi, Higashi-ku Kumamoto, Japan
c
Priority Organization for Innovation and Excellence, Kumamoto Univ., 2-39-1 Kurokami, Chuo-ku Kumamoto, Japan
*so-yoshi@kumamoto-u.ac.jp
b
Unique properties of ionic liquids (ILs), especially their wide potential window, enable us to use
ILs for understanding redox reactions of various organic molecules at potentials that unable to be
obtained in aqueous and organic solvents. From the standpoint of electrochemical surface science,
an interface between an IL and an electrode is expected to produce new organic materials by
controlling electrode potential. Here we focused on multi-step electroreduction of C60 because the
formation of its highly charged anions enables us to produce new fullerene materials at the
IL/electrode interface. Recently, we investigated multi-step electroreduction of C60 film formed on
Au(111) in two kinds of ILs [1]. In this study, we report the effect of the IL cation on multi-step
electroreduction of C60 film obtained in four kinds of ILs.
1-Butyl-3-methylimidazolium hexafluorophosphate ([C4mim][PF6]), tributylmethylammonium
bis(trifluoromethylsulfonyl)imide ([N1,4,4,4][TFSI]), N-alkyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([Cnmpyrr][TFSI]; n = 3,4), and N-butyl-Nmethylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([C4mpyrr]
[TFSI]) were used. Prior to each experimant, Au(111) electrodes were
annealed in hydrogen flame, and immersed into 50 !M C60/benzene
for 5 min. Then, the C60-modified Au(111) electrodes were transferred
to EC cell in the glovebox.
Fig. 1 shows cyclic voltammograms of C60-modified Au(111) in
each IL. A clear dependence on the IL cation was found for the redox
waves of C60 film. Only four redox waves of C60 film could be found
in both [C4mim][PF6] and [N1,4,4,4][TFSI], although the
electrochemical potential window (Epw) of [N1,4,4,4][TFSI] is wider
than that of [C4mim][PF6] and viscosities of [C4mim][PF6] and
[N1,4,4,4][TFSI] are almost the same [2]. Redox waves of C60 film were
detected up to five for [C3mpyrr][TFSI] and six for [C4mpyrr][TFSI],
respectively. On the other hand, the peak separation, "E, for each
redox wave increased in the order of [C4mim][PF6] ("E = 120 40
mV) < [Cnmpyrr][TFSI] ("E = 185 125 mV) < [N1,4,4,4][TFSI] ("E = Fig. 1.
Typical cyclic
400 50 mV). The results suggest that multi-step electroreduction of voltammograms of a clean
electrode (dashed
C60 film is independent on viscosity of IL, and both a wide Epw and the Au(111)
line)
and
C60!modified
interaction between C60 anions and IL cations are important for Au(111) electrode obtained in
(a)
[C4mim][PF6],
and
controlling the multiple redox states of C60 at room temperature.
[TFSI]!based IL (b) [N
] +,
[1] Ueda H, Nishiyama K, Yoshimoto S, Electrochem. Commun., 2014, in press.
[2] Zhang S, Lu X, Zhou Q, Li X, Zhang X, Li S, in Ionic Liquids Physicochemical
Properties, Elsevier B.V., Oxford, 2009, pp. 84, 394.
A7
1,4,4,4
(c)
[C3mpyrr]+,
(d)
[C4mpyrr]+, respectively, at 25
C. Scan Rate: 500 mV s1.
Electrochemical synthesis of silicon nanowires from an ionic liquid and their

performance as anode material
Anne Willerta,*, Sherif Zein El Abedina, Frank Endresa,
a
Institute of Electrochemistry, Clausthal University of Technology, Clausthal-Zellerfeld, 38678-Germany

*anne.willert@tu-clausthal.de
The discussion about energy storage and development of full electric vehicles lead to a worldwide
rising interest in the development of rechargeable lithium ion batteries. The problems which more
or less stopped the large scale application of current lithium ion batteries are mainly safety concerns
due to the flammable organic electrolytes. To ensure a better performance and a higher safety of
this type of battery, ionic liquids have been investigated as possible electrolytes. Investigations of
different anode materials have shown that silicon is one of the most promising host materials for
lithium with a specific capacity of up to 3579 mAh g-1 for Li15Si4.[1] Especially nanosized silicon,
e.g. nanoparticles and nanowires, can better withstand the volume change during the
charging/discharging process compared to silicon films.[2-4] Here we will report on the
template-assisted synthesis of silicon nanowires from the air- and water stable ionic liquid
1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide ([Py1,4]TFSA). The synthesis was
done by electrochemical deposition in the pores of a commercial track etched polycarbonate
membrane. After chemical dissolution of the polycarbonate membrane in dichloromethane
nanowire arrays with a regular arrangement were obtained (see image). Different lengths of
nanowires can be obtained by varying the applied potential and the time of deposition.[5] These
silicon nanowire arrays were tested as anode material in a battery set up with respect to capacity and
cycling stability against lithium. Additionally we will show first results on the fabrication of lithium
nanowires. The cycling stability is controlled by cyclic voltammetry.
References
[1] Liu XH, Zhang LQ, Zhong L, Liu Y, Zheng H, Wang JW, Cho JH, Dayeh SA, Picraux ST, Sullivan JP, Mao SX, Ye
ZZ, Huang JY, Nano Lett., 2011, 11(6):2251-2258.
[2] McDowell MT, Lee SW, Harris JT, Korgel BA, Wang C, Nix WD, Cui Y, Nano Lett., 2013, 13:758-764.
[3] Chan CK, Peng H, McIlwarth K, Zhang XF, Huggins RA, Cui Y, Nature Nanotechnology, 2008, 3:31-35.
[4] Li J, Dozier AK, Li Y, Yang F, Cheng YT, J. Electrochem. Soc., 2011, 158(6):A689-A694.
[5] Willert A, Zein El Abedin S, Endres F, Aust. J. Chem. , 2014, in press
A8
Navigating non-wetting nanoislands: A tortuous path for ionic liquid

pre-wetting films on chemically patterned mica
Zhantao Wanga and Craig Priesta*
a
Ian Wark Research Institute, University of South Australia, Adelaide, Australia

*craig.priest@unisa.edu.au
The connection between the interfacial properties of ionic liquids and their wetting behavior has
been studied very little to date and not at all on heterogeneous surfaces. We have investigated the
static and dynamic wetting for a family of ionic liquids, 1-alkyl-3-methylimidazolium
bis(trifluoromethanesulfonyl)imide, [Rmim][NTf2], on mica, where R represents an ethyl, butyl, or
hexyl alkyl chain on the imidazolium ring. A precursor film is observed to form on both
homogeneous and heterogeneous mica surfaces. The thickness of the precursor films for
[emim][NTf2], [bmim][NTf2], and [hmim][NTf2] were 0.53, 0.65, and 1.0 nm, respectively,
according to atomic force microscopy. Viscous spreading of the ionic liquid droplet on bare mica
occurs within seconds but is then followed by a very slow relaxation that can be closely correlated
with the typical time-scales of the precursor film growth. A monolayer of octadecylphosphonic acid
(OPA) on mica prevents both the formation of a precursor film and relaxation of the contact angle.
However, only a partial surface coverage of !60% OPA is required to have the same effect due to
connectivity of the nanoscale heterogeneity. Quenching of precursor film formation (and associated
contact angle relaxation) is due to an increasingly connected network of OPA regions that closes the
nanoscale paths of bare mica on which the precursor film can develop via surface diffusion.
Figure: AFM images (1 m ! 1 m) and line scans of mica modified with a 37% coverage of
octadecylphosphonic acid (OPA) islands (a) before placing the [emim][NTf2] droplet and (b) 10"20
min after placing the droplet ~ 100 m away from the scanning location (see inset), and (c) 90 min
after placing the droplet. Line scans are shown below, with the height of the OPA monolayer
(dashed line) and thickness of the fully developed precursor film (shaded) is shown in (c) and also
in (b) to compare with the partially developed precursor film after 10"20 min. Figure taken from
Ref. [1].
References
[1] Zhantao Wang and Craig Priest, Langmuir, 2013, 29: 11344-11353.
A9
Direct Synthesis of Nitrogen-doped Carbon Materials from Protic Ionic Liquids

and Protic Salts: Structural and Physicochemical Correlations between
Precursor and Carbon
Shiguo Zhang a,* Kaoru Dokko a, Masayoshi Watanabe a
a
Department of Chemistry and Biotechnology, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku,
Yokohama, 240-8501, Japan
*sgzhang@ynu.ac.jp
The traditional preparation of carbon materials requires specific polymer precursors and complex
procedures. Recently, specific cyano/nitrile-containing ionic liquids were demonstrated to be
excellent precursors due to their negligible volatility, high thermal stability, and molecular
tunability.[1,2] In this work, a series of easily prepared protic ionic liquids and salts (PILs/PSs) based
on widely obtainable N-containing bases and acids were synthesized and explored as novel
small-molecule carbonaceous precursors. Carbon materials with tunable attractive properties were
obtained via direct carbonization without any catalyst, tedious synthesis, vacuum system, and
etching step that are often involved in conventional precursors. The correlations between the
organic precursors and the properties of the carbon materials, in terms of yield, graphitization, N
content, thermal stability against oxidation, and porosity, were systematically investigated.
Importantly, certain highly porous N-doped carbon materials obtained by this one-step,
template-free method were found to show high CO2 uptake and excellent electrocatalytic
performance toward oxygen reduction reaction. These low-cost and versatile precursors are
expected to be important building blocks for carbon materials.[3,4]
References
[1] Lee J, Wang X, Luo H, Baker G, Dai S, J. Am. Chem. Soc., 2009, 131: 4596-4597.
[2] Paraknowitsch, J. P.; Zhang, J.; Su, D. S.; Thomas, A.; Antonietti, M. Adv. Mater., 2010, 22: 87-92.
[3] Zhang S, Miran M, Ikoma A, Dokko K, Watanabe M, J. Am. Chem. Soc., 2014, 136: 1690-1693.
[4] Zhang S, Dokko K, Watanabe M, submitted.
A10
Ionothermal synthesis of aluminophosphate molecular sieve membranes

Xiaolei Lia, b, Keda Lia, b, Zhijian Tiana,* Huaijun Maa, Renshun Xua, and Bingchun Wanga
a
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China

b
Universityl of Chinese Academy of Sciences, Beijing, China
*tianz@dicp.ac.cn
Introduction
Ionothermal synthesis is a promising method for the preparation of aluminophosphate molecular
sieve membranes . As a result of the negligible vapor pressure of ILs, ionothermal synthesis can
take place at ambient pressure, which eliminates safety concerns. Aluminophosphate molecular
sieve membranes of types AEL, AFI, CHA, and LTA were ionothermally synthesized on the
surface of !-alumina substrate by Substrate Surface Conversion method. X-ray diffraction (XRD),
scanning electron microscopy (SEM), diffusion reflectance Fourier transform infrared spectra
(DRIFTS) and single-gas permeation were carried out to investigate the formation mechanism of
molecular sieve membranes.
Methods
Aluminophosphate molecular sieve membranes were prepared by placing homemade -alumina
substrates in a solution of IL, phosphoric acid, hydrofluoric acid, and, if required, organic amines
without additional source of Al.
Results and discussion
Molecular sieve membranes of types AEL, AFI, CHA, and LTA can be synthesized by adjusting
the kind of ionic liquids and organic amines in the initial solution. The orientation of AEL
membranes could be modified by adjusting the addition of HF. The formation mechanism of
Substrate Surface Conversion is probably solid-solid formation mechanism. The CHA and LTA
membrane were shown to be gas-permeable (Figure 1).
Figure 1. (a) SEM image of CHA membrane (surface), (b) SEM image of CHA membrane (cross section), (c) SEM
image of LTA membrane (surface), (d) SEM image of LTA membrane (cross section), (e) Single-gas permeances of
different gases through the CHA membrane at 293 K as a functional of kinetic diameter, (f) Single-gas permeances of
different gases through the LTA membrane at 293 K as a functional of kinetic diameter.
References
[1] Li K, Tian Z, Li X, Angew. Chem. Int. Ed., 2012, 51:1-5.
[2] Cai R, Sun M, Chen Z, Angew. Chem. Int. Ed., 2008, 47:525-528.
A11
Ionic liquid, [EMIM][BF4] confined in mesoporous silica matrices: Crystallization

kinetics studies
a
Abhishek Kumar Guptaa,* Rajendra Kumar Singha and Suresh Chandraa,#

Department of Physics, Banaras Hindu University, Varanasi- 221005, India.
*abhishekgupta.bhu@gmail.com, # rksingh_17@rediffmail.com
Ionic liquid has been immobilized in mesoporous silica matrix using non-hydrolytic sol-gel process
using 1-ethyl-3-methylimidazolium tetrafluoroborate [EMIM][BF4] ionic liquid (IL), tetraethyl
orthosilicate (TEOS) as metallic precursor and formic acid as a catalyst. In the present study we
have studies the crystallization kinetics behavior of pure ionic liquid (IL)
(1-ethyl-3-methylimidazolium tetrafluoro borate; EMIMBF4) as well as IL confined in mesoporous
silica matrices (termed as ionogel). Crystallization kinetics behavior of IL in bulk as well as in
confinement has been studies using Differential Scanning Calorimtry. To study the crystallization
behavior of IL in bulk and in confinement isothermal crystallization temperatures were chosen few
C above the onset crystallization temperature. DSC have used to determined the different
crystallization kinetic parameters such as relative crystallinity (!), crystallization half time (t1/2),
crystallization rate constant (K) and Avrami exponents (n) by isothermal technique. The results of
the crystallization kinetic of IL have been found to be dependent on amount of IL and
crystallization isothermal temperatures. The confinement of the IL has been found to show one
dimensional crystallization kinetics behavior than the bulk IL (which shows three dimensional
crystallization kinetics behaviors) along with the delayed crystallization in confinement. The
delayed crystallization of IL in confinement has also been explained and confirmed by X-ray
photoelectron spectroscopy (XPS) and transient plane source (TPS) studies.
A12
Synthesis and Characterization of Renewable Ionic Liquids for Biomass

Pretreatment
Blake A. Simmonsa,b*, Aaron Sochaa,b, Jian Shia,b, Ning Suna,c, and Seema Singha,b
a
Joint BioEnergy Institute, Deconstruction Division, Emeryville, CA, USA

Sandia National Laboratories, Biological and Materials Science Center, Livermore, CA USA
c
Lawrence Berkeley National Laboratory, Physical Biosciences Division, Berkeley, CA USA
*basimmons@lbl.gov
Ionic liquids (ILs), solvents composed entirely of paired ions, have been used in a wide variety of
process chemistry and renewable energy applications. Imidazolium-based ILs show remarkable
abilities to dissolve biomass, and are thus an ideal media for biomass pretreatment and
depolymerization[1]. Although very efficient, imidazolium cations are currently expensive and
therefore their large scale use and industrial deployment, e.g. in biorefineries, is limited[2]. In an
attempt to replace imidazolium-based ILs with ILs derived from renewable sources that retain their
efficiency for biomass pretreatment, we synthesized a series of tertiary amine based ILs from
aromatic aldehydes derived from lignin and hemicellulose, the major byproducts of lignocellulosic
biofuel production. A comprehensive analysis of extractable cell wall carbohydrates and sugar
yields from switchgrass and switchgrass pretreated with tertiary amine based ILs derived from
vanillin
([Van][H2PO4]),
p-anisaldehyde
([p-AnisEt2NH][H2PO4])
and
furfural
([FurEt2NH][H2PO4]) confirmed their effectiveness for biomass pretreatment. The amounts of
sugar released by enzymatic hydrolysis of the cellulose present in switchgrass was comparable to
that obtained after pretreatment with 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]).
Enzymatic saccharification with [FurEt2NH][H2PO4] and [p-AnisEt2NH][H2PO4] provided 90% and
96% of total possible glucose and 70% and 76% of total possible xylose, respectively, after biomass
pretreatment. Computationally, [Van][H2PO4] showed the lowest net basicity, and poor lignin
removal efficiency and low sugar yields were observed experimentally. We found that
[FurEt2NH][H2PO4] and [p-AnisEt2NH][H2PO4] had higher b values and higher net basicity than
[C2mim][OAc]. Though [FurEt2NH][H2PO4] and [p-AnisEt2NH][H2PO4] were slightly less
effective towards lignin removal, sugar yields from SG pretreated with these compounds were
nearly equivalent to yields from SG pretreated with [C2mim][OAc]. Glycome profiling experiments
suggest that the biomass derived ILs [FurEt2NH][H2PO4] and [p-AnisEt2NH][H2PO4] act on plant
cell walls in a mechanism distinct from [C2mim][OAc], and studies are underway to understand
these process implications in terms of lignin and hemicellulose depolymerization and IL recycling.
These results indicate that biomass derived renewable ILs are very effective in pretreatmenting
biomass, and establish an important foundation for the further study of these unique compounds in
other industrial applications. Our concept of deriving ILs from lignocellulosic biomass shows
significant potential for the realization of a closed-loop process for future lignocellulosic
biorefineries, and has far-reaching economic impacts for other IL based process technology
currently using ILs synthesized from non-renewable sources.
References
[1] S. Singh, B. Simmons, & K. Vogel, Biotechnol Bioeng, 2009, 104(1):68-75
[2] A. Stark, Energy Environ Sci, 2011, 4:19-32.
A13
The Regeneration of Biomass Macromolecule from Ionic Liquid by using

Compressed Carbon Dioxide and Water and the Interaction Mechanism
Xiaofu Sun, Tiancheng Mu*
Department of Chemistry, Renmin University of China, Beijing, China
*Corresponding author email: tcmu@chem.ruc.edu.cn
The regeneration of biomass (chitosan, cellulose, and lignin et al.) from ionic liquid (IL) is an
important issue. Generally, the biomass can be generated from IL by adding anti-solvent, such as
water and ethanol. An efficient method to precipitate and refine chitosan[1], cellulose[2], and lignin[3]
from IL using compressed carbon dioxide was proposed. 1-butyl-3-methylimidazolium acetate
([Bmim]OAc) was used as the solvent of biomass. The interaction mechanism among carbon
dioxide (also water and other solvents for comparsion), bioamss, and IL were investigated.[4,5] The
yield and degree of polymerization (DP) value of the regenerated biomass can be finely tuned by
control of the temperature, pressure, reaction time and addition of aprotic polar solvents. For better
understanding the possible precipitation mechanism, the possible carboxylation reaction, volume
expansion and solvatochromic parameters of the solution caused by compressed carbon dixoide
were investigated. The solvent strength of the system can be adjusted by the pressure and
temperature of carbon dioxide. The regenerated samples from [Bmim]OAc by addition of different
anti-solvents were characterized by solid-state cross-polarization/magic angle spinning (CP/MAS)
13
C NMR, X-ray diffraction (XRD) spectra and atomic force microscope (AFM). In addition, the
energy consumption analysis during anti-solvent process was discussed. The precipitation and
staged bio-refinery biomass from IL is easy, sustainable and cost-efficient.
References
[1] Sun X, Xue Z, Mu T, Green Chem., 2014, 16: 2012-2016.
[2] Sun X, Chi Y, Mu T, Green Chem., 2014, DOI: 10.1039/c4gc00085d.
[3] Sun X, Mu, T, in preparation.
[4] Chen Y, Cao Y, Sun X, Mu, T, J Mol Liq., 2014, 190:150-158.
[5] Chen Y, Cao Y, Zhang Y, Mu, T, J Mol Stru., 2014, 1058: 244-251
A14
Conversion of Biomass Using Hydrophobic Ionic Liquids

Akio Kamimura a,* Kouji Kaiso,b Hiroshi Matsumoto,b Makoto Yoshimotoa
a
Department of Applied Molecular Bioscience, Yamaguchi University Ube 755-8611, Japan

b
Ube laboratory, Ube Industries, Ube 755-8611, Japan
*ak10@yamaguchi-u.ac.jp
Development of an efficient method for the conversion of biomass such as cellulose has been of
interest in current chemistry. Use of ionic liquids (ILs) is one of the most attractive methods for this
purpose because some ILs dissolve cellulose at room temperature. However, separation of the
products from the reaction mixture often provokes a formidable problem because ILs become as a
contaminant that is not easy for removal. This is because both of products of these reactions and ILs
that dissolve cellulose are water soluble. To solve the problem, we examined hydrophobic ILs as
the reaction media. In this paper we will show an efficient conversion of cellulose to glucose in
hydrophobic ILs. We will also discuss a novel conversion of sorbitol, which is available as a
biomass product, using ILs. These methods achieved not only efficient conversion but also good
separation of ILs and products. This improvement will contribute to encouragement of the use of
ILs for these purposes.
Treatment of cellulose in [TMPA][NTf2] at 100 C failed to dissolve cellulose and conversion to
glucose did not progressed. Addition of aqueous HCl and LiCl improved the reaction and the yield
of glucose reached about 50%.[1] A mixture of glucose and LiCl, no contaminant with ILs, was
isolated and purification of glucose was achieved by treatment with acetone-iPrOH mixed solvent.
[TMPA][NTf2] was recovered in more than 98% and reused for the reaction for several times.
OH
[TMPA][TFSA] (2 mL)
LiCl (1.5 g)
cellulose
12M HCl (1 mL)
0.2 g
Microwave 100 C
15 min
OH OH
HO
OH OH
sorbitol
HO
HO
O
OH
glucose; 51%
OH
1st; 42%
2nd; 44%
3rd; 43%
4th; 36%
5th; 41%
6th; 43%
recovery of IL
>98%
H OH 1st;
24% (9%)
O
2nd; 25% (10%)
OH [TMPA][TFSA]
3rd; 25% (8%)
microwave
O
4th; 24% (9%)
irradiation
H
5th; 24% (8%)
HO
270 C, 30 min isosorbide
1
recovery of IL
>96%
The yeidls of
monohydrated
sorbitol is in
parentheses
Conversion of sorbitol to isosorbide has been investigated so far and many methods have been
reported. Usually acidic conditions such as acid in water are employed for the transformation. We
are interested in using hydrophobic ILs for the conversion. Treatment of sorbitol with
[TMPA][NTf2] at 200 C under microwave irradiation resulted in the complete recovery of sorbitol.
However, the reaction performed at 270 C under microwave irradiation efficiently achieved the
conversion to isosorbide, which was obtained in 25% yield. Separation of the product from ILs was
readily achieved by a simple extraction. The ILs are recovered and used for several times.
References
[1] Kamimura A, Okagawa T, Oyama N, Otsuka T, Yoshimoto M, Green Chem., 2012, 14: 2816- 2820.
A15
Sugar-philic ionic liquids: pyrrolidinium salts with trihydroxy(phenyl)borate

Masahiro Yoshizawa-Fujita,* Erina Kishi, Yuko Takeoka, Masahiro Rikukawa
a
Department of Materials & Life Sciences, Sophia University, 7-1 Kioi-cho, Chiyoda-ku, Tokyo, Japan
*masahi-f@sophia.ac.jp
Ionic liquids (ILs) with anions such as chloride or acetate have better solubility of cellulose
as compared with that of others. However, in many systems, the solubility of cellulose dramatically
decreases in the presence of water [1]. Therefore, this is a serious problem in considering the
application of ILs to wet biomass. In order to overcome this problem, we focused on the use of
borate anions composed of boronic acid. Boronic acid interacts with saccharides in the presence of
water [2]. In this study, we synthesized pyrrolidinium-based organic salts with phenylboronic acid
and estimated the polarity of these salts to analyze the mechanism of cellulose dissolution.
Pyrrolidinium-based organic salts with phenylboronic acid as the anion
(1-butyl-1-methylpyrrolidnium trihydroxy(phenyl)borate ([BMP][PhB]) and 1-(2-methoxyethyl)-1methylpyrrolidinium trihydroxy(phenyl)borate ([MEMP][PhB])) were synthesized as shown in
Scheme 1. These salts were unstable below water content 20 wt.% probably due to the
decomposition of organic cations. Other organic cations such as imidazolium cations were unstable
even at above water content 20 wt.%. A hydroxide ion conductor based on pyrrolidinium salts with
small amount of water has been reported by MacFarlane et al [3]. Pyrrolidinium cations are a more
stable chemical structure in basic conditions.
Scheme 1 Synthesis of pyrrolidinium salts with trihydroxy(phenyl)borate.

The solubility test of cellulose was conducted in organic salt aqueous solutions at 30 C.
[BMP][PhB] and [MEMP][PhB] with water content 40 wt.% showed the highest cellulose solubility
of 3.5 and 4.0 wt.%, respectively, in this study. Introducing ether group to pyrrolidinium cation
improved the cellulose solubility. These results indicated that organic cation also affected on the
cellulose dissolution. The ! value of [BMP][PhB] with water content 40 wt.% was determined by
using solvatochromic dyes to be 0.70, which was equal to those of ILs that can dissolve cellulose.
Thus, organic salts with boronic acid group on the anion will be interesting for biomass
applications.
References
[1] M. Mazza, D. A. Catana, C. Vaca-Garcia, C. Cecutti, Cellulose, 2009, 16: 207-215.
[2] Boronic acids, ed. by D. G. Hall, Wiely-VCH, Weinheim, 2005.
[3] J. Sun, D. R. MacFarlane, M. Forsyth, J. Mater. Chem., 2001, 11: 2940-2942.
A16
From clothing to carbon fibre: Processing natural polymers using ionic liquids
Nolene Byrne
Institute for Frontier Materials, Deakin University, Waurn Ponds, Australia
nolene.byrne@deakin.edu.au
The use of natural polymers in particular natural fibres such as wool, silk and cotton has always
been important for the textile industrie. More recently natural fibres are finding increased use in
emerging industrys such as advanced composite materials for the automotive and aerospace
industries. In almost all applications natural polymers require extensive pretreatment. In this talk we
discuss the use of ionic liquids for the processsing of natural fibres.
A17
A Salty Catwalk: Ionic Liquids meet Fashion

Michael Hummela,*, Anne Michuda, Marjaana Tanttub, Shirin Asaadia, Yibo Maa, Lauri K.J. Haurua, Herbert Sixtaa
a
Department of Forest Products Technology, Aalto University, P.O. Box 16300, FI-00076 Aalto, Finland
Department of Design, School of Arts, Design and Architecture, Aalto University, P.O. Box 31000, 00076 Aalto,
Finland
*michael.hummel@aalto.fi
The constant worldwide increase in consumption goods causes an urgent demand for new
sustainable resource strategies. This also affects the textile market. The demand of cellulosic textile
fibers is predicted to increase at such a rate that it cannot be covered by cotton much longer. A
considerable shortage of 15 million annual tons of cellulosic fibers is anticipated by 2030.
Currently, man-made cellulosic fibers are produced via the viscose and Lyocell process on a
commercially relevant scale. However, both processes suffer from problems and limitations. Ionic
liquids have been proposed as alternative solvents to circumvent certain problems associated with
the existing processes. The solubility of cellulose in certain ILs has been demonstrated already more
than a decade ago[1] followed by reports on the solubilization of even complex biopolymer matrixes
such as wood.[2,3] However, all studies available on the subsequent shaping of the biopolymer
solution into textile fibers exclusively use imidazolium-based ILs with halide or carboxylate anions.
ILs comprising of imidazolium cations and nucleophilic anions have been shown to have limited
thermal stability and degrade the cellulosic solute.[4] This causes severe problems when aiming for a
large scale process.
Herein we present a non-imidazolium based ionic liquid, 1,5-diazabicyclo[4.3.0]non-5-enium
acetate,[5] as excellent solvent for cellulose fiber spinning. Various solutes from dissolving pulp,
unbleached kraft pulp, and even cellulosic waste material such as waste paper and card board could
be dissolved in high concentration up to 19 wt-% at moderate temperature and within short
dissolution time. Fibers could be spun at low process temperatures which prevented cellulose
degradation. The solutions showed outstanding spin stability allowing the filaments to be stretched
to a factor of almost 20. This led to fibers with excellent tensile strength surpassing commercial
Lyocell fibers and suitable for composite material and textile applications. The latter has been
demonstrated in collaboration with a renowned Finnish textile and clothing design company. A
prototype dress made of birch wood dissolving pulp has been manufactured via IL-fiber spinning
and was exhibited at the autumn-winter fashion show. Thus, the applicability of ILs on large scale
was tested.
References
[1] Swatloski RP, Spear SK, Holbrey JD, Rogers RD, J. Am. Chem. Soc., 2002, 124: 4974-4975.
[2] Pinkert A, Marsh KN, Pang S, Staiger MP, Chem. Rev., 2009, 109: 6712-6728.
[3] Brandt A, Grasvik J, Hallett JP, Welton T, Green Chem., 2013, 15: 550-583.
[4] Wendler F, Todi L-N, Meister F, Thermochim. Acta, 2012, 528: 76-84.
[5] Parviainen A, King AWT, Mutikainen I, Hummel M, Selg C, Hauru LKJ, Sixta H, Kilpelaeinen I, ChemSusChem,
2013, 6: 2161-2169.
A18
Utilization of AmineOrganic Superbase derived Switchable Ionic Liquid (SILs)

as Solvent in an Optimal Delignification Process
Ikenna Anugwom,a Valerie Eta,a Pasi Virtanen, a Pivi Mki-Arvela,a Kari Ernen,a
and Jyri-Pekka Mikkola a,b
a
Laboratory of Industrial Chemistry and Reaction Engineering, Process Chemistry Centre, bo Akademi University
,bo-Turku, 20500 (Finland)
b
Technical Chemistry, Department of Chemistry, Chemical-Biological Center, Ume University, SE-901 87, Ume, Sweden
*ianugwom@abo.fi
Introduction
The need to develop new economical and feasible conversion/fractionation techniques in order to
yield value-added products from lignocellulosic material is burgeoning. Several attempts have been
made throughout the years and several promising processes and solvents have been suggested.
Typical limitations are coupled to the cost of the whole process. An unconventional and economical
feasible fractionation method for wood chips using e.g. an alkanol amine (monoethanol amine,
MEA) and an organic superbase (1,8-diazabicyclo-[5.4.0]-undec-7-ene, DBU), derived Switchable
Ionic Liquid (SIL)[1-2] was developed while the optimal conditions for cost attractive conditions was
studied in a batch system[3] (Fig 1). Herein a novel cascade flow through reactor setup which can be
used to carry out experiments in 1-2 liter scale (liquid phase) is introduced. The reactor setup is
equipped with an accurate control and measurement of flow rate, temperature and pressure as well
as flexible 5-point sampling of liquid and solid phases (Fig 2).
0.8
PI
untreated birch
STHT treated birch
Gaussian fit functions
sum of Gaussian fit
100
80
0.6
60
0.4
0.2
0.0
TIC
40
Collector vessel
Differential Mass Fraction
1.0
20
0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5
Log Molar Mass
2000
1500
1000
500
-1
wavenumber (cm )
The removal of the acetylated hemicelluloses

from wood (pectins)
PI
1
TIC
TIC
TIC
TIC
TIC
FI
Fig. 2 A cascade flow through reactor

setup
Fig.1 Results from the batch system using SILs as solvents.

References
[1] Anugwom I., Mki-Arvela P., Virtanen P., Damlin P., Sjholm R., Mikkola J.-P. 2011, RSC Advances, 1, 452-457.
[2] Jessop P.G., Heldebrant D.J., Xiaowang L., Eckert C.A., Liotta C.L. 2005, Nature, 436(25), 1102.
[3] Anugwom I, Eta V, Virtanen P., Mki-Arvela P., Hedenstrm M., Hummel M.,Sixta, H., Mikkola , J.-P., 2014,
Chemsuschem, Doi:10.1002/cssc.201300773.
A19
Hydrolysis of cellulose catalyzed by novel acidic ionic liquids

Kelei Zhuo*, Quanzhou Du, Congyue Wang, Yujuan Chen, Guangyue Bai, Jianji Wang
Henan Normal University, Xinxiang, China
*klzhuo@263.net
Cellulose as a widespread renewable resource in nature has wide scope of applications. The
products obtained from cellulose degradation, such as reducing sugar and 5-hydroxymethylfurfural,
are important organic chemical raw materials and intermediates. And converting cellulosic biomass
directly into energy material and functional materials using chemical method and modern physical
technology becomes a hot subject.[1] Ionic liquids (ILs) have many advantages, such as low vapor
pressure, good thermal stability and regulated function, and thus can be used as solvents and
catalysts in the hydrolysis of cellulose because they have good performances for the dissolution of
cellulose.[2, 3]
In this work, a series of SO3H-functionalized ionic liquids based on 2-Phenyl-2-imidazoline (Fig.1)
were synthesized and used as catalysts for the hydrolysis of cellulose. And the acidity, thermal
decomposition temperature and structure of the acidic ionic liquids were investigated and
characterized by UV-VIS, TGA and NMR. The acidic ionic liquids were investigated as catalysts
for the hydrolysis of cellulose in [Bmim]Cl. The effect of acidity, amount of water and reaction
conditions including reaction temperature and reaction time on the yield of total reducing sugar
(TRS) were also investigated. The experimental results suggested that the acidic ionic liquids with
anions HSO4! and Cl! showed good effects on the hydrolysis of cellulose (Fig.2). The appropriate
temperature and dosage of water affected significantly the yield of total reducing sugar. When the
hydrolysis of cellulose was catalyzed by 1-propyl sulfonic acid-2-phenyl imidazoline
hydrogensulfate (IL-1), the TRS yield was up to 64.7%. The new approach opens a way for the
conversion of cellulose to available chemical raw materials.
TRS
50
Yield/M%
40
30
20
10
None
IL-1
IL-2
IL-3
IL-4
IL-5
IL-6
ILs
Fig.1 The structures of ILs in this work
Fig.2 Yields of TRS catalyzed by various ILs
Acknowledgement: Financial supports from the National Natural Science Foundation of China
(Nos. 21173070, 21303044) and the Plan for Scientific Innovation Talent of Henan Province (No.
124200510014) are gratefully acknowledged.
References
[1] Liu Y., Xiao W., Xia S., et al. Carbohydr. Polym., 2013, 92(1): 218-22.
[2] Cole A. C., Jensen J. L., Ntai I., et al. J. Am. Chem. Soc., 2002, 124(21): 5962-3.
[3] Swatloski R. P., Spear S. K., Holbrey J. D., et al. J. Am. Chem. Soc., 2002, 124(18): 4974-5.
A20
Recent Developments with Triaminocyclopropenium Ionic Liquids

Owen J. Curnow,* Chaminda Jayasinghe, Kelvin J. Walst and Ruhamah Yunis
Department of Chemistry, University of Canterbury, Private Bag 4800, Christchurch 8140, New Zealand
*E-mail: owen.curnow@canterbury.ac.nz
Triaminocyclopropenium salts are readily prepared

from commercially-available C3Cl5H and the
desired secondary amine. These salts have been
found to have high thermal stabilities
(decomposition onset temperatures of up to 400
C), good electrochemical windows, and
reasonable viscosities[1].
In an effort to reduce molecular weights and lower
viscosities, reduced-symmetry cations were
prepared via alkylation of the cyclopropenone[2]. It
was
found
that
the
resultant
alkoxydiaminocyclopropenium
cations
react
readily with secondary and primary amines,
including amino acids, to give new aprotic and
protic ILs, respectively. The amino acids lead to
chiral protic ILs.
In this presentation, I will discuss further work on the properties and potential uses of these
materials. This includes miscibility/solubility studies, chemical stability studies, use in cellulose
dissolution/regeneration and uses in chiral synthesis.
References
[1] Curnow OJ, MacFarlane DR, Walst KJ, Chem. Commun., 2011, 47: 1024810250.
[2] Curnow OJ, Holmes MT, Ratten LC, Walst KJ, Yunis Y, RSC Adv., 2012, 2: 1079410797.
A21
Ionic Liquids Tailored for Biomolecular Interaction Analysis and

Chemoselective Gas Sensing
Ming-Chung Tseng and Yen-Ho Chu*
Department of Chemistry and Biochemistry
National Chung Cheng University, Chiayi 62102, Taiwan, ROC
cheyhc@ccu.edu.tw
This work highlights our recent progress on ionic liquid research.[1-3] Ionic liquids are organic salts
and many of them are liquid at ambient temperature.[1] Compared with conventional molecular
solvents, ionic liquids carry a number of attractive properties such as remarkable solubility with
small molecules, good thermal stability, high polarity and conductivity, and negligible vapor
pressure that are suited for a myriad of favorable applications, including reaction media for organic
synthesis, affinity interaction analysis of peptides and small proteins, chemoselective gas sensing,
electrolytes for rechargeable lithium ion batteries, solvents for cellulose dissolution, and PCR
enhancers for DNA amplification.[1,2]
Ionic liquids offer a platform of tunable structures on which properties and functions of both cation
and anion can be independently engineered. We have employed, for example, affinity ionic liquids
and sensing ionic liquids to explore functionalized ionic liquids through incorporation of functional
groups as a part of developing ionic liquids possessing tailored properties. In this work, we are to
describe our recent development of chemically stable ionic liquids and their applications for
chemoselective gas sensing by quartz crystal microbalance (QCM),[3] affinity extraction of peptides
and proteins, and PCR amplification of DNA.
References
[1] For our recent reviews on ionic liquids, see: (a) Sowmiah S, Cheng C, Chu Y-H, Curr. Org. Syn., 2012, 9: 74-95;
(b) Sowmiah S, Srinivasadesikan V, Tseng M-C, Chu Y-H, Molecules, 2009, 14: 3780-3813.
[2] (a) Tseng M-C, Chu Y-H, Anal. Chem., 2014, 86: 1949-1952; (b) Liu Y-L, Tseng M-C, Chu Y-H, Chem.
Commun., 2013, 49: 2560-2562; (c) Shi Y, Liu Y-L, Lai P-Y, Tseng M-C, Tseng M-J, Li Y, Chu Y-H, Chem.
Chemmun., 2012, 48: 5325-5327; (d) Tseng M-C, Cheng H-T, Shen M-J, Chu Y-H, Org. Lett., 2011, 13:
4434-4437; (e) Chen C-W, Tseng M-C, Hsiao S-K, Chen W-H, Chu Y-H, Org. Biomol. Chem., 2011, 9:
4188-4193; (f) Tseng M-C, Chu Y-H, Chem. Commun., 2010, 4: 2983-2985; (g) Tseng M-C, Tseng M-J, Chu
Y-H, Chem. Commun., 2009, 7503-7505.
[3] Cheng C, Chang Y-P, Chu Y-H, Chem. Soc. Rev., 2012, 41: 1947-1971.
A22
Paramagnetic Ionic Liquids from Cationic Metal-Chelate Complexes

Tomoyuki Mochida,* Megumi Okuhata, Yusuke Funasako
Department of Chemistry, Kobe University, Kobe 657-8501, Japan
*tmochida@platinum.kobe-u.ac.jp
In recent years, various interesting magnetic ionic liquids have been prepared. We have developed
ionic liquids containing metallocenium cations,[1] and these liquids exhibit unusual magnetic
responses[2] and chemical reactivities. Herein, we report on the preparation and properties of a series
of metal-containing paramagnetic ionic liquids that contain cationic chelate complexes.
[Fe(acacen)(1-butylimidazole)2][Tf2N] (1-Tf2N) is a blue paramagnetic liquid at room temperature,
and it only undergoes a glass transition at low temperature (Tg = 242 K).[3] The temperature
dependence of the magnetic moment of this liquid is shown in Figure 1 (left). This liquid exhibited
a spin-crossover phenomenon, and a rapid decrease in magnetic susceptibility was observed when it
was cooled from room temperature to ~200 K. Furthermore, this liquid showed thermochromism, in
which its color reversibly changes between blue-green (below 250 K) and violet-blue (above 300
K). For comparison, the crystal structures and magnetic properties of 1-PF6 were investigated. The
magnetic
susceptibility
of
this
salt
closely
resembled
that
of
1-Tf2N.
[Co(acacen)(1-butylimidazole)2][Tf2N] was a red-brown diamagnetic solid with a melting point of
348 K.[4] This salt exhibited a glass transition at 268 K upon cooling from the melt.
[M(R1-acac)(R2-diamine)][Tf2N] (M = CuII, NiII) are ionic liquids that change color when exposed
to organic vapors with coordination abilities.[5] The change was caused by coordination of the vapor
molecules
to
the
cation.
The
II
Cu -containing liquids were paramagnetic,
whereas the NiII-containing liquid changed
from diamagnetic to paramagnetic after
absorbing vapors. The NiII-containing
liquid exhibited thermochromism and a
temperature dependent magnetic moment
after absorbing methanol.
Fig. 1. (left) Structural formula of 1-Tf2N. (right) Magnetic susceptibilities of 1-Tf2N. The inset
shows the photographs of 1-Tf2N at 248 K and 313 K.
References
[1] Inagaki T, Mochida T, Takahashi M, Kanadani C, Saito T, Kuwahara D, Chem. Eur. J., 2012, 18: 6795-6804.
[2] Funasako Y, Mochida T, Inagaki T, Sakurai T, Ohta H, Furukawa K, Nakamura T, Chem. Commun., 2010, 47:
4475-4477.
[3] Okuhata M, Funasako Y, Takahashi K, Mochida T, Chem. Commun., 2013, 49: 7662-7664.
[4] Okuhata M, Mochida T, J. Coord. Chem., in press.
[5] Funasako Y, Mochida T, Takahashi K, Sakurai T, Ohta H, Chem. Eur. J., 2012, 18: 11929-11936.
A23
Evaluation of 100 kt/a Composite Ionic Liquid Alkylation (CILA) Plant

Rui Zhang, Zhichang Liu*, Xianghai Meng, Haiyan Liu and Chunming Xu
State Key Laboratory of Heavy Oil Processing, China University of Petroleum(CUP), Beijing, China
* lzch@cup.edu.cn
Chloroaluminate ionic liquids (ILs) [1] were discovered as potential alternatives for the traditional
isobutane alkylation catalysts (HF and H2SO4). A composite ionic liquid (CIL) developed by China
University of Petroleum[2] shows good catalytic performance for isobutane alkylation. In August
2013, the first commercialized 100 kt/a CILA plant was succesfully started-up in Shandong Deyan
Chemical Co., Ltd.. By far, the plant has been running stably over 180 days. This plant includes
four sections, namely feed treatment, staged reactors, reactor refrigeration and product treatment. In
addition, this plant also has CIL handling facilities to enable solids removal and CIL regeneration.
On January 14th-17th, 2014, CPCIF (China Petroleum and Chemical Industry Federation)
organized experts to conduct a 72-hour on-site plant evaluation. During this time, the typical
composition of C4 feed lists in Table 1. The evaluation showed that: the olefin conversion was
100%; the alkylate yield was 80% of feed; the average RON of alkylate was 96.8; the catalyst
consumption per ton alkylate was 5 kg; the energy consumption per ton alkylate was 157 kgEO
(including a selective hydrogenation unit to remove diolefins and to convert 1-butene to 2-butene, a
small hydrogen manufacturing unit and the whole plant utilities). Table 2 shows the mass balance in
this 72 hours. The evaluation concluded that the CILA plant showed better safety and
environmental benefits compared with HF and H2SO4 alkylation processes.
Table 1 Composition of C4 feed in volume
propane
propene
isobutane n-butane t-2-butene 1-butene isobutene c-2-butene
1.44%
0.75%
40.32%
17.91%
14.19%
11.85%
0.43%
11.86%
dimethyl
ether
butadiene isopentane n-pentane methanol
Total sulfur
others
Total
0.22%
0.64%
0.05%
0.09%
0.18%
2.36 ppm
0.07%
100%
72 hours evaluation
C4 feed
alkylate
n-butane
propane
othersi-butane, loss
Total
Table 2 Mass balance of CILA plant

inlet, t
outlet, t
yield, %
Acknowledgement: Financial
820
support was provided by
656
80.0
Shandong Deyang Chemical
132
16.1
Co. Ltd, Dongying, China. The
10
1.2
research is financially supported
22
2.7
by the National Science
820
820
100
Foundation of China (Grant
Nos. 21036008, 21276275, 21206193), PetroChina, and SSR (Shell Research Fund), The
Netherlands.
References
[1] Chauvin Y., Einloft S., Olivier H., Ind. Eng. Chem. Res., 1995, 34: 1149-1155.
[2] Liu Z., Xu C. M., Huang C. P., US20040133056A1.
A24
Parallel Lectures B
Manipulating Hydrogen Bond Complexes in Ionic Liquids to Facilitate the

Purification of Pharmaceuticals
Cameron C. Webera, Andreas J. Kunov-Krusea, Robin D. Rogersb and Allan S. Myersona*
a
Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA 02139
b
Department of Chemistry, The University of Alabama, Tuscaloosa, AL, USA 35487
*myerson@mit.edu
The flexibility of ion selection for ionic liquids (ILs) makes these compounds attractive as solvents
for purification processes due to the possibility of tailoring the solvent to the substrate of interest. In
particular, the ability to form hydrogen bond complexes due to either cationsolute or anionsolute
interactions can significantly enhance the solubility of compounds bearing hydrogen bond acceptor
or donor groups within IL solvents.[1,2,3]However, for the IL solvent to be effective at purifying a
given compound it is important that the compound is also able to be recovered with reduced
impurity concentration in a reasonable yield. Furthermore, the incorporation of the solvent in the
final product needs to be minimized, a non-trivial consideration given the non-volatility of ILs.[3]
This presentation will outline our investigation into the selection of appropriate IL solvents for the
purification of active pharmaceutical ingredients (APIs), including our studies on the role of
hydrogen bond complexes on solubility and the nature of these hydrogen bonding interactions. The
ability to disrupt these complexes through a judicious choice of antisolvent to effect the purification
of the API will be discussed, along with the resultant influence on the purity and yield of the
product. Finally, the significance of these findings for the purification of other related compounds
will be addressed.
References
[1] Moniruzzaman M and Goto M, J. Chem. Eng. Jpn., 2011, 44: 370-381.
[2] Swatloski R P, Spear S K, Holbrey J D and Rogers R D, J. Am. Chem. Soc., 2002, 124: 4974-4975.
[3] Wang H, Gurau G, Kelley S P, Myerson A S and Rogers R D, RSC Adv., 2013, 3: 10019-10026.
B1
Novel Choline Derivative Ionic Liquids for the Extraction of Drug Molecules
Zhiyong Li, Jing Liu, Yuanchao Pei, Jianji Wang*
Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, Key Laboratory of
Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Henan
Normal University, Xinxiang, Henan 453007, P. R. China
* jwang@henannu.edu.cn
Ionic liquids (ILs) have numerous potential applications in industrial processes as a benign
alternative to conventional solvents.[1] However, many of them are toxic to organisms and are
poorly biodegradable, such as imidazolium and pyridinium based ILs.[2] An alternative approach for
overcoming these drawbacks is the development of ILs from their components which have well
characterized biodegradable and toxicological properties.[3] In this context, green feature of ILs has
been improved by making ILs from choline derivatives, these ILs are thus expected to have
biodegradable characteristics and high biocompatibility.
In this work, 16 kinds of choline derivative ILs with choline structure as cations and
bis(trifluorosulfonyl)imide as anion have been synthesized and characterized. Chemical structures
of these ILs are shown in Scheme 1. All of these ILs are liquid at room temperature and immiscible
with water. Thus these ILs have been utilized for the extraction/separation of 3 kinds of drug
molecules from aqueous solutions by simple IL/water biphasic systems. The main observations of
the present work are as follows.
anion
cations
H
HO
OH
OH
HO
R
[CnDEA]+
OH
NH
R
[CnMDEA]+
OH
R
HO
[CnBDEA]+
S
R
F3C
OH
S
O
CF3
[CnDIPA]+
Scheme 1. Chemical structures of choline derivative ionic liquids

1. These ILs were found to be excellent extractants for the drug molecules studied. Under the
optimized conditions, partition coefficients for the most of the drug molecules were greater than 2.
Partition coefficients of the drug molecules increase with increasing temperature, and the
electrostatic interactions between the IL and ciprofloxacinHCl played an important role in the
extraction process.
2. For a given IL, partition coefficients of the drug molecules decreased in the order:
ciprofloxacinHCl > tetracyclineHCl > 4-acetamidophenol, and hydrophobicity of the drug
molecules is the main factor affecting the partitioning of drug molecules in ILs-water biphasic
systems.
References
[1] N. V. Plechkova, K. R. Seddon, Chem. Soc. Rev., 2008, 37, 123-150.
[2] K. J. Kulacki and G. A. Lamberti, Green Chem., 2008, 10, 104-110.
[3] Z. Li, X. Liu, Y. Pei, J. Wang, M. He, Green Chem., 2012, 14, 2941-2950
This work was supported financially by the National Natural Science Foundation of China (No.21133009, 21273062)
and the Science and Technology Research Key Project of Henan Educational Committee (13A150511).
B2
Removing benzothiophene from model oil in the presence of aromatic

hydrocarbons using 1-butyl-3-methylimidazolium ionic liquid
Syamsul B. Abdullaha* and Zakaria Manb
a
Faculty of Chemical and Natural Resources Engineering, Universiti Malaysia Pahang,

Lebuhraya Tun Razak, 26300 Gambang, Pahang, Malaysia.
b
PETRONAS Ionic Liquid Centre, Chemical Engineering Department, Universiti Teknologi PETRONAS,
Bandar Seri Iskandar, 31750, Tronoh, Perak, Malaysia.
*syamsul@ump.edu.my
In the process of organosulfur removal from petroleum products using ionic liquids (ILs), the
organosulfur compounds may form a weak linkage with ILs through !-! interaction. However,
aromatic hydrocarbons which are parts of petroleum product constituents may interrupt this !-!
interaction, and consequently, affect the separation efficiency. Thus, the current study was
conducted to investigate the possible application of ILs in removing organosulfur compound in the
presence of aromatic hydrocarbons in n-dodecane (n-C12) as model oil. In this study, it was found
that 1-butyl-3-methylimidazolium octylsulfate ([bmim][OSO4]) with longer alkyl chain length on
the anion site gave better benzothiophene (BT) extraction with 63% removal while the miscibility
study shows that benzene and toluene are completely miscible, whereas xylene formed partial
miscibility with [bmim][OSO4]. When the extraction were conducted on BT/benzene, BT/toluene
and BT/xylene mixtures in n-C12, the [bmim][OSO4] showed remarkably higher in partition ratio
(KD) value for BT with 1.7 whereas benzene, toluene and xylene gave 0.6, 0.3 and 0.2 respectively.
These results suggest that [bmim][OSO4] will not only extract BT, but also will remove a certain
amount of aromatic hydrocarbons from hydrocarbon phase during the desulfurization process.
Keyword: selectivity, benzothiophene, aromatic hydrocarbon, [bmim][OSO4], desulfurization
O
80
O-
S
O
O
% removal
60
(iii)
O-
40
(ii)
20
HO
O-
(i)
0
Figure 1: Effect of different anions of imidazolium-based sulfate ILs in the extractive desulfurization as (i)
1-butyl-3-methylimidazolium hydrogen sulfate; (ii) 1-butyl-3-methylimidazolium methyl sulfate and (iii)
1-butyl-3-methylimidazolium octylsulfate
Extraction conditions: room temperature; mass ratio model fuel oil to IL = 1/1; extraction time 10 minutes; initial benzothiophene concentration,
95050ppm.
References
[1] E!er J, Wasserscheid P, Jess A, Green Chem., 2004, 6: 316-322.
[2] Syamsul A, Man Z, Bustam M.A, J. Chem., 2013, 838590.
B3
Separation of BTEX Aromatics from n-Octane Using a Deep Eutectic Solvent

Experiments and COSMO-RS prediction
Mohamed K. Hadj-Kalia, Sarwono Mulyonoa, Hanee F. Hizaddinb, Mohd A. Hashimb, Inas M. Alnashefa
a
King Saud University, Chemical Engineering Department, Riyadh, Saudi Arabia

University of Malaya, Department of Chemical Engineering, Kuala Lumpur, Malaysia
* mhadjkali@ksu.edu.sa
Separation of aromatics from aliphatics is a challenging process because of the close range of their
boiling points and the formation of several combinations of azeotropes. Until now, no feasible
separation process is available for aromatic concentrations below 20 wt%. However, because of
their negligible vapour pressure and many other advantages, ionic liquids and deep eutectic solvents
(DESs) have been reported as potential solvents in a liquid-liquid extraction process for this
purpose.
In this work, we have investigated the possibility of using a selected DES for the liquid-liquid
extraction of benzene, toluene, ethylbenzene and m-xylene (BTEX) aromatics from n-octane. The
DES used was synthesized by combining tetrabutylammonium salt and sulfolane. Sulfolane was
selected as complexing agent due to its high selectivity for aromatics. Equilibrium data for the
ternary system consisting of BTEX aromatics, n-octane and DES were measured at 25C and
atmospheric pressure. The ability of the synthesized DES to selectively extract aromatics from a
mixture of aromatic and aliphatic compounds was proven. Indeed, the results showed that the
proposed DES has comparable distribution ratio and selectivity to those of commercial solvents.
Moreover, sulfolane was not found in the raffinate phase, for all tested systems. This remarkable
finding will undeniably facilitate the separation protocol and hence reduce the cost of the separation
process.
The performance of COSMO-RS to predict ternary LLE diagrams for systems with DES was
evaluated for the first time and it was observed that the prediction by COSMO-RS only agrees
qualitatively with the experimental tie lines and the trend for distribution ratio and selectivity.
Furthermore, the experimental data were satisfactorily correlated using the NRTL model, showing
that this classical model can easily be adopted with systems including Deep Eutectic Solvents.
Figure 1. Ternary phase diagram for n-octane + ethylbenzene + DES at 25C. The full symbols and solid lines represent
experimental data, empty circles and dotted lines represent NRTL correlation, triangles and dashed lines represent
COSMO-RS prediction.
B4
Thermal behavior of Concanavalin A Dissolved in Hydrated Cholinium

Dihydrogen Phosphate
Kyoko Fujitaa,b,c, Ayano Takasakid, Yoko Fujita-Yamaguchid and Hiroyuki Ohnoa,b,c
a
Department of Biotechnology, bFunctional Ionic Liquid Laboratories, cJapan Science and Technology Agency (JST),
Core Research for Evolutional Science and Technology (CREST), Tokyo University of Agriculture and Technology,
2-24-16 Nakacho, Koganei, Tokyo 184-8588, Japan
d
Department of Applied Biochemistry school of Engineering, Tokai University, 1117 Kitakaname, Hiratsuka, Kanagawa
259-1292, Japan
*kyokof@cc.tuat.ac.jp
We have proposed hydrated ionic liquids (Hy-ILs) as solvents for biomolecules. Hy-ILs are easily
prepared by mixing the ILs with small amount of water, but the mixture maintains basic property of
the ILs. Furthermore, some Hy-ILs have been revealed to have excellent solubility of proteins. A
coupling of cholinium cation ([ch]) and dihydrogen phosphate anion ([dhp]) provided unique Hy-IL
which had superior affinity with proteins [1]. Improvement of thermal stability and storage stability
of proteins dissolved in Hy[ch][dhp] have been reported [2]. In this work, we have investigated
thermal behavior of concanavalin A dissolved in Hy[ch][dhp].
[ch][dhp] was mixed with small amount of water in which three water molecules per ion pair.
Concanavalin A (ConA) was prepared as an aqueous solution with 10 mg/ml. The Hy[ch][dhp] was
mixed with the ConA solution at final water contents of 35 wt% in which seven water molecules
existed per ion pair. The folding state of ConA dissolved in Hy[ch][dhp] was analyzed with
fluorescence spectroscopy. A BIAcore biosensor was used
to investigate affinity between ConA and BSA antibody.
(a)
Fluorescence spectra have suggested that ConA dissolved

in Hy[ch][dhp] showed unfolding and refolding behavior
repeatedly depending on the heating and cooling,
respectively. The binding ability of ConA with BSA was
highly maintained after the thermal treatment at 70 oC. On
the other hand, the binding ability has been lost when
ConA was dissolved in buffer and treated with the same
procedure (Fig. 1).
(b)
Fig. 1 Binding affinity after treatment

at 70 oC for 10 mins in (a) Hy[ch][dhp]
and (b) buffer.
References
[1] K. Fujita and H. Ohno, Biopolymers, 2010, 93: 1093.
[2] K. Fujita, D.R. MacFarlane, M. Forsyth, M. Yoshizawa-Fujita, K. Murata, N. Nakamura and H. Ohno,
Biomacromolecules, 2007, 8: 2080.
B5
H-NMR Study on Interaction of [C4mim]Cl-Water-Guaiacol Ternary System

Kunlan Lia,* Guoliang Gonga,* Ligang Weia,* Yingchong Maa,* Yachen Yua, Jing Xianga
a
School of light Industry and Chemical Engineering, Dalian Polytechnic University, Dalian, China,116034
*likl@dlpu.edu.cn, ligonggl@sina.com, weilg@dlpu.edu.cn, 11374757@qq.com
In previous work[7-8] biomass can be treated with [C4mim]Cl-water mixture to selectively dissolve lignin and leave
cellulose as solids. In order to explain the dissolution mechanism, the model chemical of lignin, guaiacol, was
used to form ion liquids-water-guaiacol ternary system and 1H-NMR were recorded under different ion liquids
concentration in fixed guaiacol concentration and under different guaiacol concentration in fixed ion liquids-water
solution.
The self aggregation of [C4mim]Cl in water at 1.5mol/L to 105.1mol/L were investigated by 1H-NMR
measurements at room temperature, as well as the dissolution mechanism of guaiacol in [C4mim]Cl-water system.
The micelle of [C4mim]Cl will combine together to form large clusters if the concentration is higher than
22.3mol/L. From the 1H-NMR spectrum of 0.08mol/L guaiacol in [C4mim]Cl-water solution at different
concentration, it can be concluded that guaiacol would substitute the position of water in the [C4mim]Cl-water
cluster and form hydrogen bond with Cl- and C4(5)-H. And the addition of guaiacol to [C4mim]Cl-water mixture
will increase the aggregation trend of cluster as shown in Fig1 and Fig2.
H
H
H
O
H
H
H
H
Cl
H
O
N
OCH3
H
N
O
OCH3
H
Cl-
N
H
O
H
H
N
Cl
H
H
H 3CO
ClO
O
H
Cl-
O
H
O
H
Fig.2 Shielding effect of guaiacol and imidazol
H
O
Cl-
Cl-
H
H
Cl-
Fig. 1 Cluster structure of Guaiacol-[C4mim]Cl
OCH3
H
H
O
H
N
H
N
Cl-
Cl
H
H
Cl-
H
O
H
OCH3
H
O
Fig. 3 Cluster structure of [C4mim]Cl-guaiacol-water system
In order to further investigate the interaction of guaiacol to [C4mim]Cl-water system, the 1H-NMR of different
concentration of guaiacol in [C4mim]Cl-water solution was determined in XIL=0.13. The data also give evidence
of the substitution of water with phenol, as shown in Fig 3.
In conclusion, 1H-NMR is used to investigate the relationship of [C4mim]Cl-water system and [C4mim]Cl-waterguaiacol system. In [C4mim]Cl-water system, there are ion liquids in water solution when XIL is lower than 0.29,
while there are water in ion liquids solution when XIL is higher than 0.29. When phenol (guaiacol) is added to the
ion liquid-water system, phenol can substitute the water to form hydrogen bond with ion liquids to increase its
solubility in the solution, which can explain the selective dissolution of lignin from biomass.
References
[1] Wei Ligang, Li Kunlan, Ma Yingchong, Hou Xiang, Industrial Crops and products, 2012, 37: 227-234
[2] Wei Ligang, Ma Yingchong, Li Kunlan, Wang Jilei, Yu Yachen, Applied Mechanics and Materials, 2012,
217-219:993-996.
[3] Mara G. Freire, Catarina M. S. S. Neves, Pedro J. Carvalho, Ramesh L. Gardas, Ana M. Fernandes, Isabel M.
Marrucho, Luis M. N. B. F. Santos, Joao A. P. Coutinho, J. Phys. Chem. B, 2007, 111:13082-13089
[4] Marijana Blesic, Maria Helena Marques, Natalia V. Plechkova, Kenneth R. Seddon, Luis Paulo N. Rebelo, Antonio
Lopes, Green Chem., 2007, 9:481490
[5] Corine Tourne-Peteilh, Jean-Marie Devoisselle, Andre Vioux, Patrick Judeinstein, Martin Inc, Lydie Viau, Phys.
Chem. Chem. Phys., 2011, 13:1552315529
B6
Alcohol in Protic Ionic Liquids: Dissolution or Self-Assembly?

Haihui Joy Jianga, Rob Atkinb, Paul FitzGeralda, Gregory Warra*
a
The School of Chemistry, The University of Sydney, Sydney, Australia

Priority Research Centre for Advanced Particle Processing and Transport,
Protic ionic liquids (PILs) are capable of segregating into hydrophobic and hydrophilic domains,
forming a sponge-like nanostructure. We have studied the structural changes induced in a series of
PILs by addition of n-alcohols using Small and Wide Angle X-ray Scattering (SAXS/WAXS).
Mixtures of ethylammonium, ethanolammonium and propylammonium formate (EAF, EtAF, and
PAF) and nitrate (EAN, EtAN and PAN) are examined with a series of n-alcohols (CnH2n+1OH, n =
2, 4, 6, 8, 10, 12) in which they exhibit widely differing and temperature-dependent miscibilities.
In miscible systems, the nanostructure of the PIL alcohol mixtures is determined by the size of the
alcohol alkyl chain relative to the IL cation alkyl chain. For example, ethanol in EAN induces a
small increase in the low q scattering (Figure 1a), which indicates a minor rearrangement of the
solution structure. In comparison, larger scale structures are observed with the addition of n-hexanol
(Figure 1b), with low-angle scattering reminiscent of either micelle formation or possibly a
bicontinuous microemulsion.
We have also studied the effect of changing the cations and anions of ionic liquids with the addition
of n-alcohols. EtAN and EtAF are immiscible with even moderate chain-length alcohols. With the
addition of any given n-alcohol, the extent of structural change in EAF is less than EAN. PAN is
more miscible with longer chain alcohols, and it enables the formation of larger-scale structures.
Non-monotonic changes in peak postion at lower q scattering are observed as a function of alcohol
concentrations. In general, the average size of the large-scale structures reaches a maximum at
40-60 wt% alcohol in a given ionic liquid.
This study shows that the strong cohesive forces present in ILs can induce self assembly of
molecules that do not self assemble in water, paving the way to new nanostructured fluids.
4
10
-3
9
8
7
6
EAN
20%
60%
90%
5
4
10%
40%
80%
Ethanol
Intensity (arb. units)
Intensity (arb. units)
-2
10
EAN
20%
60%
90%
(b) Hexanol in EAN
(a) Ethanol in EAN
8
6
10%
40%
80%
Hexanol
2
-3
10
6
4
6 7 8 9
6 7 8 9
10
6 7 8 9
4
-1
-1
6 7 8 9
10
q / nm
q / nm
Figure 1. SAXS/WAXS
data of (a) ethanol, and (b) n-hexanol added to ethylammonium
nitrate (EAN).
B7
Designing Ionic Liquids for Highly Efficient and Selective Capture of H2S
You-Ting Wua,* Kuan Huanga, Xing-Bang Hua
a
School of Chemistry and Chemical Engineering, Nanjing Univerisity, Nanjing, P.R.China

*ytwu@nju.edu.cn
Abstract The selective capture of hydrogen sulfide (H2S) is one of the most important topics
involving energy conservation and emission reduction in the field of energy processing and
utilization[1]. The methods currently available for H2S capture in industry usually have some serious
problems, such as high energy consumption, low selectivity in separating H2S from carbon dioxide
(CO2), and large volatile loss of absorbents to cause environmental pollution. Ionic liquids (ILs), as
a kind of molten salts with unique properties, have been shown to be candidating absorbents for
H2S capture from the research work in recent years[2]. However, there are still few efforts in
designing task-specific ionic liquids for the selective capture of H2S. In view of the different
characteristic of H2S molecule from CO2 molecule, we proposed to use dual Lewis-base
functionalized ionic liquids (DLB-ILs) to develop novel and creative methods for the selective
capture of H2S (as shown in Figure 1). Due to the polar property of H2S molecule and the presence
of active protons in H2S molecule, DLB-ILs have great affinity with H2S. Therefore, the absorption
capacity for H2S in DLB-ILs is enhanced significantly in relative to other ILs. However, CO2
molecule is nonpolar and there are not active protons in CO2 molecule. As a result, DLB-ILs could
only interact with CO2 through very weak Lewis acid-base interaction and the absorption capacity
for CO2 in DLB-ILs is limited to a very low level. Thus, not only high absorption capacity for H2S
but also high absorption selectivity for H2S/CO2 are achieved in DLB-ILs. We demonstrated the
underlying mechanism for the different dissolution behaviour of H2S and CO2 in DLB-ILs through
thermodynamic modeling and quantum chemical calculations.
Figure 1. Demonstration of the selective absorption of H2S in DLB-ILs

References
[1] Pomelli CS, Chiappe C, Vidis A, Laurenczy G, Dyson PJ, J. Phys. Chem. B., 2007, 111:13014-13019.
[2] Huang K, Cai DN, Chen YL, Wu YT, Hu XB, Zhang ZB, AIChE. J., 2013, 59: 2227-2235.
B8
High Throughput Synthesis and Characterisation of Protic Ionic Liquids

Tamar Greavesa,b*, Krystal Hab, Ben Muirb, Shaun Howardb, Calum Drummonda
a
RMIT University, Melbourne, Australia

CSIRO Materials Science and Engineering, Melbourne, Australia
*Tamar.Greaves@csiro.au
Protic ionic liquids (PILs) are a subset of ionic liquids which are easily synthesised through the
stoichiometric combination of a Brnsted acid and a Brnsted base. They are of interest for a broad
range of applications, including as solvents/catalysts for organic or inorganic synthesis, electrolytes
for fuel cells, lubricants, amphiphile self-assembly media and as additives for biological
applications such as biocatalysis, protein crystallisation and stabilisation.
There is growing interest in PILs instead of aprotic ILs primarily due to their low cost and ease of
synthesis, while still maintaining many of the key properties of aprotic ILs, such as low or
negligible volatility and melting points < 100 oC. Like ionic liquids in general, there is a vast
number of possible cation-anion combinations which can results in PILs, making them a highly
tailorable class of solvents which can be optimised for a broad range of applications. However, to
date there have only been around 500-600 PILs reported in the literature. In addition, most
investigations into PILs for specific applications include only a very small subset of the known
PILs.
We have developed a high throughput synthesis route for PILs using the isynth reactor with a
ChemSpeed robotic platform. In a trial study we have produced a series of 48 PILs using the robot,
from 6 alkylamines and 8 carboxylate anions. To the best of our knowledge this is the first high
throughput synthesis of ionic liquids. For the synthesis the base was maintained at 3 oC in stirred
reactor vials, and the acid was mixed with methanol and added dropwise. The methanol and water
were removed under vacuum using the isynth reactor.
Visual screens were applied to the samples to classify them as liquid, gel or solid at room
temperature, and to classify their viscosity as low, medium or high. The mesostructure of the 48
PILs was characterised using the SAXS/WAXS beamline at the Australian Synchrotron. The water
content of each sample was measured using the conventional Karl Fischer technique.
We believe that high throughput synthesis and characterisation techniques are essential to enable
screening of a broad range of PILs for specific applications. In addition, we envisige that high
throughput synthesis would be of significant benefit for producing mixtures of protic or aprotic ILs
combined with conventional molecular solvents.
B9
Hydrogen Bonding Interactions between 1-Ethyl-3-methylimidazolium

Bis(trifluoromethylsulfonyl)imide and Acetonitrile
Yu Zhou, Yan-Zhen Zheng, Zhi-Wu Yu*
Department of Chemistry, Tsinghua University, Beijing 100084, P. R. China
E-mail: yuzhw@tsinghua.edu.cn
Hydrogen bonds play a key role in the physicochemical properties of ILs and co-solvents. The
properties of ILs and their mixtures with co-solvents are largely related with the strength and the
number of hydrogen bonds. Studies on hydrogen bonding interactions between ILs and co-solvents
are of great importance. In this work, the interactions between 1-ethyl-3-methylimidazolium
bis(trifluoromethylsulfonyl)imide ([Emim][Tf2N]) and CH3CN have been investigated by
attenuated total reflection (ATR) infrared spectroscopy, nuclear magnetic resonance (NMR), and
density functional theory (DFT) calculations. Excess infrared spectroscopy, developed in our
laboratory[1,2], was also used to analyze the
infrared spectra.
Deuterated acetonitrile was used in the IR
study to avoid the overlap in the CH stretching
vibration region of [Emim]+ cation and
acetonitrile. The partial ATR-FTIR and excess
infrared spectra in the CH and S=O stretching
vibration regions are shown in Figure 1. The
!(aromatic CH) is red-shifted, while !(S=O) is
blue-shifted with increasing CH3CN. The excess
bands in Figure 1B,D are nearly fixed in the
concentration range investigated, indicating that
the interaction pairs are stable. For the 1H NMR
data all the hydrogen atoms on [Emim]+ move
downfield with increasing CH3CN, while the
hydrogen atoms on CH3CN move upfield with
Figure 1. ATR-FTIR (A,C) and excess infrared
increasing [Emim][Tf2N].
spectraB,Din the CH and S=O stretching vibration
Combining the results of ATR-FTIR, 1H
region.
NMR, and DFT, we conclude: 1) The
hydrogen bonds involving aromatic CH in the [Emim]+ are strengthened when adding acetonitrile.
2) The hydrogen bonding effect is the dominant factor for the chemical shift changes of the
hydrogen atoms. Acetonitrile moleculars would like forming hydrogen bonds rather than
aggregation with itself. 3) Acetonitrile cannot break apart the strong Coulombic interaction between
[Emim]+ and [Tf2N]" by simple insertion between them.
References
[1] Li QZ, Wu GS, Yu ZW, J. Am. Chem. Soc., 2006, 128: 1438-1439.
[2] Li QZ, Wang NN, Zhou Q, Sun SQ, Yu ZW, Appl. Spectrosc., 2008, 62: 166-170.
B10
Bio-inspired Ionic Liquids Containing Transition Metal Functional Groups for

CO2 Capture
Junhua Huanga;* Hanming Liua b, Andrew Wardenc; Anthony E. Rosamiliaa; Phillip Pendletonb
a
Energy Technology, CSIRO, BOX 312, Clayton South, VIC 3169, Australia
Center for Molecular and Materials Sciences, Sansom Institute, University of South Australia, Adelaide, SA 5000,
Australia
c
CSIRO Ecosystem Sciences - Black Mountain Laboratories Clunies Ross Street, Black Mountain ACT 2601, Australia
* Corresponding author: Jewel.Huang@csiro.au.
b
Ionic liquids (IL) are considered as promising CO2 absorbents in CO2 capture and storage processes
due to their intrinsic selectivity towards CO2 over other gases as well as their high thermal and
chemical stabilities and low volatility.[1] Previously we reported introducing transition metal salts,
known for their affinity towards CO2 in carbonic anhydrase, into ILs as an effective method to
improve CO2 absorption capacity.[2, 3]
In this work we investigated CO2 absorption mechanism in an example IL
1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([Emim][Tf2N]) containing
ZnTf2N salt. In neat [Emim][Tf2N], DFT calculations show that the free rotation of the Tf2N- anion
around the C-S-N-S dihedral causes steric hindrance to CO2 association. In the presence of Zn2+ the
coordination with Tf2N- holds the nitrogen in an exposed geometry, allowing its lone pair to
associate weakly with CO2. We further studied the influence of water on ionic arrangement and
CO2 interactions. Water is incorporated in the system as interlaying water, coordinated water,
hydrogen bonded water and free OH. Ionic arrangement is highly dependent on the content of
water, which is also reflected in water-dependent phase transitions. H2O plays a key role to stabilise
absorbed CO2 to form bicarbonate, in a similar way as in carbonic anhydrase, and thus improves the
CO2 solubility. E.g. an [Emim][Zn(Tf2N)3]2H2O complex uptakes 1.2 CO2 at 1 bar and 40 oC. In
contrast the CO2 uptakes in anhydrous [Emim][Tf2N] and [Emim][Zn(Tf2N)3] are 0.03 and 0.3
(mol:mol CO2:IL) respectively.
The influence of cations and anions were studied. Their physical properties, CO2 absorption
behaviour including absorption kinetics will be reported. The implication of these properties in
practical CO2 capture processes will be discussed.
References
[1] Huang J, Rther T, Aust. J. Chem., 2009, 62: 298-308.
[2] Huang J, Rther T, Feron P, Zhang Z, WO Patent 2011/011830 A1.
[3] Liu H, Huang J, Pendleton P, Energy Procedia 2011, 4: 59-66.
B11
The effect of ionic liquids in aqueous multiphase liquid-liquid equilibrium

system
Liang Yuwen, Xu Shouhong, Shang Yazhuo*, PengChangjun, Liu Honglai
Key Laboratory for Advanced Materials and Department of Chemistry,
East China University of Science and Technology, Shanghai 200237, China
* Corresponding author, E-mail: shangyazhuo@ecust.edu.cn
The effect of ionic liquids on aqueous multi-phase system of DTAB/SDS/PEG/NaBr/H2O has been
studied by displacing the inorganic salt NaBr partially or completely with short chain ionic liquids
(1-ethyl-3-methyl imidazolebromine [C2mim]Br, 1-butyl-3-methyl imidazole bromine [C4mim]Br)
and the cationic surfactant DTAB with long chain ionic liquid (dodecyl-3-methyl imidazole
bromine [C12mim]Br). The results have shown that the formation of aqueous four-phase system of
DTAB/SDS/PEG/NaBr/H2O are the result of the coexistence of "polymer ATPS" and "surfactant
ATPS ". The stonger hydrophilic nature of short chain ionic liquids ([C2mim]Br[C4mim]Br)
endows their stonger salting out ability, which ensured the existence of polymer ATPS in aqueous
four-phase system. The interaction between ionic liquids and polymer and the effect of ionic liquids
on the interaction among surfactants can not be neglected because all of them have prominent
influence on the phase behavior of mixed system and the properties of the coexisted multi-phase.
The long chain ionic liquid [C12mim]Br affects the properties of "surfactant ATPS " by
hydrophobic effect and act as the role of surfactant. However, the difference of molecular structure
between [C12mim]Br and DTAB leads to the redistribution of surfactant molecules in two phases
of "surfactant ATPS". Correspondingly, the volumes and extraction ability of the two phases are
changed. Obviously, aqueous multiphase system with specific properties could be obtained by tailor
the alkyl chain length and adjust the content of ionic liquids in mixed systems.
Visually apparent phenomenon (a) and apparent

phenomenon observed under polarization device (b)
of the system of
0.2MSDS/0.2MDTAB/PEG/NaBr/H2O
T=313K, CT =0.2M, R=2.04, PEG%=0.7%.
The extraction of four phase systems of

SDS/DTAB/PEG/NaBr(C2min)/H2O to xylenol
orange, CT=0.2MT=313KR=2.04
PEG%=0.7%
B12
Absolute pKa Calculation of Benzoic Acid and Benzenethiol in

Room Temperature Ionic Liquid
Xiao-Song Xue,* Ya Wang, ZhenWang, Xin Li*
Engineering (Tianjin), and College of Chemistry, Nankai University, Tianjin, China
*Corresponding authors e-mail address: xuexs@nankai.edu.cn; xin_li@nankai.edu.cn
Knowledge of the pKa value of Brnsted acids is fundamentally important for understanding
the chemistry in solution. Because the acidic dissociation equilibrium of an acid strongly depends
on the nature of medium,[1] the pKa quantity can also provide valuable information on the effect of
specific solvation. In this line, we have recently initiated a project to experimentally measure the
standard and absolute pKa values in pure ionic liquids (ILs)[2], with an aim to use pKas as a tool for
probing the so-called ionic liquid effects.
It is quite interesting to note that the relative acidity order of benzoic acid and benzenethiol in
DMSO is different from that in water.[3] The reversed order of the observed acidity changes has
been interpreted by considering the better solvation of the aprotic DMSO solvent molecule for
thianion than for oxanion.[4] Recently, we found that the relative order of the absolute pKa values of
benzoic acid and benzenethiol in the "aprotic" ionic liquid [Bmim][NTf2] is the same as that in
water. In order to understand the "unexpected" acidity order in ILs, we carried out the present
computational study.
In this work, we have performed the first calculation of their absolute pKa values in ionic media.
The experimental pKas of benzoic acid and benzenethiol in ionic liquid [Bmim][NTf2] are well
reproduced by theoretical calculation. Multiple C-HO and C-HS hydrogen bonds are relevant to
the origin of the acidity order for benzoic acid and benzenethiol in [Bmim][NTf2].
Compounds
pKa
in H2O
pKa
in DMSO
pKa
in [Bmim][NTf2]
Referenc
es
[1] Taft R
W,
Bordwell
F
6.6
10.3
17.2 (Calc. 17.4)
G,
Acc.
Chem. Res.
1988, 21,
4.2
11.0
15.2 (Calc. 14.5)
463-469
[2]
(a)
Deng H, Li
X, Chu Y, He J Q, Cheng J P, J. Org. Chem. 2012, 77, 7291-7298. (b) Wang Z, Deng H, Li X, Ji P J, Cheng, J P, J.
Org. Chem. 2013, 78, 12487-12493.
[3] Bordwell F G, Acc. Chem. Soc. 1988, 21, 456-463.
[4] Bordwell F G, Hughes D L, J. Org. Chem. 1982, 47, 3224-3232.
B13
Stability of Glyme-Li Complex in Solvate Ionic Liquid

Seiji Tsuzukia,* Wataru Shinodab, Kazuhide Uenoc, Toshihiko Mandaic, Shiro Sekid, Soshi Saitoe, Hiroyuki Doie,
Yasuhiro Umebayashie, Kaoru Dokkoc, Masayoshi Watanabec
a
Nanosystem Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1
Umezono, Tsukuba, Ibaraki 305-8568, Japan
Graduate School of Engineering and School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya,
464-8603, JAPAN
c
Department of Chemistry and Biotechnology, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku,
Yokohama 240-8501, Japan
Materials Science Research Laboratory, Central Research Institute of Electric Power Industry (CRIEPI), 2-11-1
Iwado-kita, Komae, Tokyo 201-8511, Japan
Graduate School of Science and Technology Niigata University 8050, Ikarashi, 2-no-cho, Nishi-ku, Niigata City,
950-2181, Japan
*e-mail address: s.tsuzuki@aist.go.jp
Certain equimolar mixtures of glyme and Li salts are liquids at ambient temperature, and their
properties (ionic conductivity, negligible vapor pressure and low flammability) are similar to typical
room temperature ionic liquids. The equimolar mixtures are composed of glyme-Li complex
(Figure 1) and anion. They are categorized into solvate ionic liquids. The equimolar mixtures
are expected as electrolyte for Li-sulfur batteries due to the low solubility of lithium polysulfide in
the equimolar mixtures.[1] Although many studies were reported on the solvate structures and
liquid properties of the equimolar mixtures, it is still unclear why stable glyme-Li complexes exist
in the equimolar mixtures.
In this study we studied the stability of the solvate ionic liquid by first principle molecular
dynamics simulations. The energies of two liquid structures (solvate ionic liquid and concentrated
solution) were compared. The simulations show that the solvate ionic liquid is stabilized by the
interaction between the Li+ and glyme, while the concentrated
solution, in which Li salt is dissolved in glyme, is stabilized by the
interaction between the Li+ and anion. Although the interaction
between the Li+ and anion is stronger than that between Li+ and
glyme in the gas phase, [2,3] the solvate ionic liquid is more stable
in the condensed phase. The relationship between the interactions
between isolated species and the stable liquid structure will be
discussed based on the molecular dynamics simulations and ab Figure 1 Stable structure of
glyme-Li complex
initio calculations.
References
[1] Ueno K, Park J-W, Yamazaki A, Mandai T, Tachikawa N, Dokko K, Watanabe M, J. Phys. Chem. C, 2013,
117:20509-20516.
[2] Tsuzuki S, Hayamizu K, Seki S, Ohno Y, Kobayashi Y, Miyashiro H, J. Phys. Chem. B, 2008, 112: 9914-9920.
[3] Tsuzuki S, Shinoda W, Seki S, Umebayashi Y, Yoshida K, Dokko K, Watanabe M, ChemPhysChem, 2013, 14:
1993-2001.
B14
Water-Mediated Polymorphs in Room Temperature Ionic Liquids: Confined

Water and Hierarchy Structure
Hiroshi Abea, *, Takahiro Takekiyob, Tomonori Hanasakic, Yukihiro Yoshimurab
a
Department of Materials Science and Engineering, National Defense Academy, Yokosuka, 239-8686, Japan
b
Department of Applied Chemistry, National Defense Academy, Yokosuka, 239-8686, Japan
c
Department of Applied Chemistry, Ritsumeikan University, Kusatsu, 525-8577, Japan
*ab@nda.ac.jp
Functional water molecules behave flexiblly at each enviroment such as a chameleon.

Particulary in room temperature ionic liquids (RTILs), intrinsic water properties are well extracted.
For instance, various hydrogen bondings of water, which depends on water concentration, are
obtained by Raman spectroscopy[1]. While, hierarchy structure of the RTILs-water mixtures is
clarified by UV-vis, small-angle scattering and diffraction[2].
Very recently, confined water (water pocket) in the RTIL was experimentally observed by a
complementary use of small-angle X-ray scattering (SAXS) and small-angle neutron scattering
(SANS)[3]. The RTIL is 1-buthyl-3-methylimidazolium nitrate, [C4mim][NO3]. In the
[C4mim][NO3]-D2O mixtures at water-rich region, the water pocket is detected directly using the
different scatering cross section between X-ray and neutron. The distinct peak in SANS implies the
existence of the water pocket. The water pocket is visuallized by the simulations referring the
observed peak in SANS (Fig. 1). The average size of the confined water is estimated to be 3 nm.
This size can explain refolding of proteins in the [C4mim][NO3]-D2O mixtures[4]. The demonstrated
water pocket is quite similar to the aggregation simulated by the molecular dynamics[5] in
[C8mim][NO3]-H2O, where the water aggregations are formed near the nano-domain boundaries.
Hierarchy
structure
appears
in
N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammoniu
m
tetrafluoroborate
([DEME][BF4])-water
[2]
mixtures . Self-assembled aggregations, water
network over the medium-range, nearly free
hydrogen bonding (NFHB) of water, proton transfer
and hydration are keywords for formation of the
hierarchy structure. At around 85 mol% H2O, the
RTIL-based properties change to the water-based
ones. At the crossover point (xc = 85 mol%),
hierarchy structure appears relating with
Fig. 1 Simulated confined water using
anomalous macroscopic properties. This is
SANS profile.
regarded as a typical competing system on each
scale.
[1] Abe H, Yoshimura Y, Imai Y, Goto T, Matsumoto H, J. Mol. Liq., 2009, 150:1621.
[2] Aono M, Imai Y, Ogata Y, Abe H, Goto T, Yoshimura Y, Takekiyo T, et al., Met. Mater. Trans., 2011, 42A:37-40
[3] Abe H, Takekiyo T, Shigemi M, Yoshimura Y, et al. J. Phys. Chem. Lett. 2014, 5:1175!1180.
[4] Takekiyo T, Yamazaki K, Yamaguchi E, Abe H, Yoshimura Y, J. Phys. Chem. B, 2012, 116:11092!11097.
[5] Jiang W, Wang Y, Voth G A, J. Phys. Chem. B, 2007, 111:4812!4818.
B15
Molecular dynamics simulation of ionic liquids electric double layer structures

Maolin Shaa,*, Fabao Luoa, Qiang Doub, Guozhong Wub
a
Deparment of Chemistry & Chemical Engineering,Hefei Normal University, Hefei 230061, China
Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai201800, P.B. Box 800-204, China
*Corresponding authors e-mail address (franksha@aliyun.com)
The electric double layer structures of ionic liquids (ILs) at various electrode surfaces have recently
become an important topic of research in view of their promising applications in supercapacitors
and various electrochemical devices. However, ILs as infinite-concentration electrolytes is hard to
depict these ILs/electrode system in classical electrochemical theories which hinger on a
dilute-solution approximation. Recently, several theory models were proposed[1,2]; many
experiments[3,4] were conducted to speculate the electric double layer structures at various electrode
surfaces. The employment of polycrystalline electrode in these experiments and the lack of
molecular level structure at single-crystalline electrode add complexities for precise analysis and
theoretical modeling.
In this work, using molecular dynamics simulation, we first obtained a molecular scale picture of
electric double structures for IL BmimPF6 at a single-crystalline Au(100) electrode surface, and
comparing with the experimental results. Our simulations reveal that the strong ion adsorption
interactions between the ions and the Au electrode surface are mainly in determining the behavior
of differential capacitance. This strong adsorption layer results in an overscreening effect in the first
screening layer, finally induce the potential of zero charge moving toward the positive potentials.
We also farther demonstrated that the differential capacitance can be tuned in different curves, i.e.
bell-shape curve or camel-shape curve by the competition effect between the ion-surface adsorption
and the ions association. The specific adsorption always induces a bell-shape curve of differential
capacitance; on the contrary, the strong ions association always results in a more complicated
camel-shape curve of differential capacitance.
These unexpected results may provide hints for the possible manipulation of ILs or electrode
surface for use in supercapacitors and electrochemical devices. Our results are also important for
the fundamental understanding of the ILs or IL infinite-concentration electrolyte properties as they
are widely applied in electrochemistry and fuel cell technology.
References
[1] (a)Kornyshev, A. A., J. Phys. Chem. B, 2007, 111:5545-5557. (b)Fedorov, M. V. and Kornyshev, A. A., J. Phys.
Chem. B, 2008, 112: 11868-11872.
[2] Vatamanu, J., Borodin, O. and Smith, G. D., J. Am. Chem. Soc., 2010, 132, 1482514833.
[3] Gnahm, M., Pajkossy, T. and Kolb, D. M., Electrochimi. Acta, 2010, 55: 6212-6217.
[4] (a)Alam, M. T., Islam, M. M., Okajima, T. and Ohsaka, T., J. Phys. Chem. C, 2007, 111:18326-18333. (b) ibid., J.
Phys. Chem. C, 2008, 112: 16600-16608. (c).ibid., J. Phys. Chem. C, 2009, 113: 3386-3389.
B16
A novel approach to organocatalyst design: incorporation of an imidazolium

group as a functional catalyst component.
Luke C. Henderson,a,b* Hannah L. Brozinski.b
a
Institute for Frontier Materials, Deakin University, Geelong, Australia, 3216.

Strategic Research Center for Chemistry and Biotechnology, Deakin University, Geelong, Australia, 3216.
* luke.henderson@deakin.edu.au
The development of organocatalysts bearing an imidazolium group is becoming more common in

catalyst design as it allows for fine tuning of catalyst properties such as melting point, solubility and
recoverability.1-4 The imidazolium group on these catalysts are generally located far from the
catalytic site (as shown in compounds 1-3, below) and serves only as a means to manipulate catalyst
properties.
This talk will present the design, synthesis and preliminary evaluations of novel organocatalysts
incorporating the imidazolium group through the C-terminus of L-proline. The goal of this project
is to develop a range of tailorable organocatalysts which facilitate asymmetric transformations in
low catalytic loadings (< 5 mol%), high stereopurity (ee and de > 90%) and are able to be recovered
using the unique properties imparted by the imidazolium salt.
The potential for the imidazolium N-substituent (above in blue) to participate in the catalytic
transition state will also be investigated.
References
[1] W. Maio, T. H. Chan., Adv. Synth. Catal., 2006, 348, 1711
[2] J. Shah, S. S. Khan, H. Blumenthal, J. Liebsher, Synthesis, 2009, 23, 3975
[3] S. V. Kochetkov, A. S. Kucherenko, G. A. Kryshtal, G. M. Zhdankina, S. G. Zlotin, Eur. J. Org. Chem., 2012, 7129.
[4] Hannah. L. Brozinski, Joshua. P. Delaney, Luke C. Henderson, Aust. J. Chem. 2013, 66, 844847
B17
Isomerisation of terpene oxides over supported ionic liquid catalysts

Eero Salminena*, Pasi Virtanena, Johan Wrna, Tapio Salmia and Jyri-Pekka Mikkolaa,b
a
bo Akademi University, Department of Chemical Engineering, Process Chemistry Centre, Industrial Chemistry &
Reaction Engineering, FI-20500 bo/Turku, Finland.
b
Ume University, Department of Chemistry, Chemical-Biological Centre, SE-90187 Ume, Sweden.
*eesalmin@abo.fi
Renewable terpenes, the main components of resins, as well as their corresponding epoxides (e.g. !,
"-pinene oxides) are important precursors for the flavor and fragrance industry. Lewis acid
promoted isomerisation of !-pinene oxide results in campholenic aldehyde which is an intermediate
for the manufacture of sandalwood-like fragrances such as santalol. In the case of "-pinene oxide
as a starting material, Lewis acid catalyzed isomerisation leads to valuable perfumery compound
myrtanal [1,2]. The isomerisation of !- and "-pinene oxide was studied over supported ionic liquid
catalysts (SILCAs) containing Lewis acidic species in an immobilised ionic liquid.
Several different Lewis acids and ionic liquids were studied in terpene oxide isomerisation
reactions. Tin chloride (SnCl2) was found as the, so far, most efficient Lewis acid catalyst in
campholenic aldehyde production whereas zinc chloride was the most efficient catalyst for myrtanal
production. Deactivation of the catalysts was also studied upon recycling of catalysts in consecutive
experiments. The catalytic activity was only slightly deteriorating from batch-to-batch and most of
the deactivation occurred from the first to the second run. Decreasing specific surface areas and
pore volumes of the spent SILCAs indicated that some reaction products were accumulating into
the ionic liquid layer. Consequently, this was clearly one of the primary reasons for catalyst
deactivation. Moreover, no leaching of ionic liquid or metal chlorides was detected upon
High-Performance Liquid Chromatography (HPLC) and Inductively Coupled Plasma Mass
Spectrometry (ICP-MS) analysis.
Isomerisation of terpene oxides to value added compounds could be carried out by applying Lewis
acidic SILCAs. Activity and selectivity of the SILCA catalysts were dependent upon the nature of
ionic liquid. Over selected SILCAs, 65% and 68% molar yields of campholenic aldehyde and
myrtanal, respectively, were obtained. In fact, reusable ionic liquid modified catalysts with high
activity were accomplished. In the final paper, kinetic model of the isomerisation reaction will be
introduced.
References
[1] Chapuis C, Jacoby D, Appl. Cat. A. 2001, 221:93-117.
[2] Corma A, Renz M, Susarte M, Top. Catal. 2009, 52:1182-1189.
B18
Ionic Rh-complexes ligated by phosphine-functionalized ionic liquids: syntheses,

characterization, and catalysis to hydroformylation of 1-octene
Shengjie Chen, Shijun Lai, Haihong Wu, Yong Lu, Xiaoli Zhao, Ye Liu*
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Chemistry Department of East China Normal
University, Shanghai 200062, P.R. China
*Corresponding authors e-mail address: yliu@chem.ecnu.edu.cn
Non-volatile ionic liquids (ILs) can be functionalized flexibly by varying cations and/or anions that
constitute ILs structure with specific functionalities. Thus, it is possible to develop abundant
functionalized ILs (FILs) dually possessing the characters of the incorporated functionalities as well
as those of the ILs[1]. The phosphine-FILs have long been investigated for the design of the ionic
organometallates and application to homogeneous catalysis[2,3]. Recently, the hybrid phosphine
ligands that contain significantly different types of hard (N-, O-, S-) and soft (P-) donor functions
have attracted much attention due to their hemilabile nature. These ligands possess one weakly
coordinating group that can reversibly release during the catalytic cycle providing unsaturation site
at the metal centres, which can significantly tailor the activity of the transition metal catalysts[4].
Herein, the P,N-, P,O, and P,N,O-hybrid ligands are respectively grafted into the structures of the
ILs to develop a series of hybrid phosphine-FILs, which are applied to construct the rhodium
complexes as the efficient catalysts for hydroformylation of 1-octene. The as-synthesized
hybrid-ligand FILs and the corresponding Rh-complexes (Scheme 1) were characterized by 1H
NMR, 31P-NMR, and single crystal X-ray diffraction.
Me
PPh2
Me
Rh(CO)2(acac)
n-Bu
Me
N
PPh2
Rh(CO)2(acac)
N+
Ph
N+ n-Bu
FIL-1
PF6-
Me
OC
Ph
RhI
Me
O
OC
Ph
RhI
Me
N
Ph
BF4-
N+
BF4-
1A
Me
PF6-
2A
Me
FIL-2
Me
PPh2
Me
N+
SO3-
Rh(CO)2(acac)
Me
N
FIL-3
OC
Ph
RhI
P
O
O
3A
Ph
Me
N+
SO3PPh2
N
N+
FIL-4
SO3-
Rh(CO)2(acac)
Me
OC
Ph
RhI
N
N
O
O
Ph
4A
Me
N+
SO3-
Scheme 1 Syntheses of the rhodium complexes ligated by the phosphine-FILs
References
[1] Liu Y, Wang S, Liu W, Wan Q, Wu H, Gao G, Curr. Org. Chem., 2009, 13: 1322-1346.
[2] You HX, Wang YY, Zhao XL, Chen SJ, Liu Y, Organometallics, 2013, 32, 2698-2704.
[3] Chen SJ, Wang YY, Yao WM, Zhao XL, VO-Thanh G, Liu Y, J. Mol. Catal. A: Chem., 2013, 378, 293-298.
[4] Zotto AD, Zangrando E, Baratta W, Felluga A, Martinuzzi P, Rigo P, Eur. J. Inorg. Chem., 2005, 4707-4714.
B19
Ionic Liquid Catalyzed CO2 Conversion under Mild Conditions

Zhimin Liu*, Yanfei Zhao, Bo Yu
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Colloid, Interface and Chemical
Thermodynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
*liuzm@iccas.ac.cn
CO2 is not only the main greenhouse gas, but also a cheaper and abundant C1 resource. Conversion
of CO2 into high value-added chemicals is of great importance from both theoretical and practical
viewpoints, which has attracted much attention in recent years. However, the conversion of CO2 is
difficult, especially under mild conditions, due to its thermodynamic stability and kinetic limitations.
Ionic liquids (ILs) provide new opportunities for CO2 capture and conversion because of their
unique features such as high thermal and chemical stability, negligible vapor pressure, easy
recyclability, and tunable properties, and have widely investigated.
Herein, I will present our recent progress on CO2 conversion catalyzed by ILs. We designed
some task-specific ILs, which showed high efficiency for catalysing CO2 conversion under mild
conditions. For example, a CO2-reactive protic ionic liquid (PIL), [HDBU+][TFE-], was designed by
neutralization of a superbase 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) with a weak proton donor
trifluoroethanol (TFE). As a bifunctional catalyst for simultaneously activating CO2 and the
substrate, this PIL displayed excellent performance for catalysing the reactions of CO2 with
2-aminobenzonitriles at atmospheric pressure and room temperature, producing a series of
quinazoline-2,4(1H,3H)-diones in excellent yields.[1] In another work,[2] several DBU-based ILs
were synthesized, and applied in the synthesis of 2-benzimidazolones via the carbonylation of
o-phenylenediamines with CO2. It was indicated that DBU acetate ([DBUH][OAc]) displayed high
efficiency for catalyzing the reactions of CO2 with o-phenylenediamines, and a series of
benzimidazolones were obtained in high yields. It was demonstrated that [DBUH][OAc] served as a
bifunctional catalyst for these reactions with cation activating CO2 and anion activating
o-phenylenediamines.
References
[1] Zhao Y F, Yu B, Yang Z Z, Zhang H Y, Hao L D, Gao X, Liu Z M, Angew. Chem. Int. Ed., 2014, 53: in press.
[2] Yu B, Zhang H Y, Zhao Y F, Chen S, Xu J L, Hao L D, Liu Z M, ACS Catal., 2013, 3: 2076-2081.
B20
Ionic liquid-based thermoelectrochemical cells for harvesting waste heat

Jennifer M. Pringlea, Theodore J. Abrahamb and Douglas R. MacFarlaneb
a
!ARC Centre of Excellence for Electromaterials Science, Deakin University, 221 Burwood Highway, Burwood, VIC
3125, Australia.
b
!ARC Centre of Excellence for Electromaterials Science, School of Chemistry, Monash University, Wellington Road,
Clayton, VIC 3800, Australia

*j.pringle@deakin.edu.au
Waste heat is an abundant but underutilised source of sustainable energy. For example, use of waste
heat from power stations could generate sufficient electricity in-situ to offset some of the power
demands for applications such as lighting. Thermoelectrochemical cells are based on an alternative
design to the traditional semiconductor-based thermoelectric devices as they use an electrolyte
containing a redox couple. The electrochemical potential of this redox couple depends on
temperature, and therefore in a device with two electrodes held at different temperatures a potential
difference is created. Thus, these cells allow direct thermal to electrical energy conversion with no
carbon emissions.
Until recently, research into thermoelectrochemical cells had primarily focused on aqueous
electrolytes, predominantly with the ferri/ferrocyanide redox couple.[1] However, the good thermal
and electrochemical stability, non-volatility and non-flammability of many ionic liquids makes
them promising alternative electrolytes for these devices. Potential advantages include increased
thermoelectrochemical device efficiencies, longer lifetimes and the ability to utilise waste heat
sources in the 100 200 oC temperature range.
The magnitude of the temperature dependence of a redox couple in the ionic liquids is given by the
Seebeck coefficient, Se. Here we discuss our research into the influence of different ionic liquids on
the Se of a variety of redox couples, and how this changes the thermoelectrochemical device
performance. We will also present our recent results with the Co(II/III) redox couple,[2] which have
produced the highest power outputs to-date for thermoelectrochemical cells using ionic liquid
electrolytes.
References
1. Hu, R., Cola, B. A., Haram, N. et al., Nano Lett. 2010, 10: 838846.
2. Abraham, T. J., MacFarlane, D. R., Pringle, J. M. Energy and Environ. Sci. 2013, 6: 2639 2645
B21
N-donor functionalised room temperature ionic liquids: their thermo-physical,

electrochemical and transport properties
Thomas Rthera*, Kenneth R. Harris b*, Michael D. Hornec, Mitsuhiro Kanakubod, Theo Rodopoulosc,
Jean-Pierre Vederc, Lawrence A. Woolfb
a
Commonwealth Scientific and Industrial Research Organisation (CSIRO), Energy Technology, Clayton, Australia
School of Physical, Environmental and Mathematical Sciences, University of New South Wales, ADFA, Canberra,
Australia
c
Commonwealth Scientific and Industrial Research Organisation (CSIRO), Process Science and Engineering, Australia
d National Institute of Advanced Industrial Science and Technology (AIST), Sendai, Japan
*thomas.ruether@csiro.au
b
Ionic liquids bearing functional groups that can be tailored for specific tasks (task-specific ILs) are
interesting contenders for a range of applications but in many cases their properties have not been
studied in great detail. To take advantage of their particular properties and versatility it is important
to obtain an understanding of structurephysicochemical property relationships. Properties
measured for the N-donor functionalised ionic liquids (1) and (2) were the electrochemical window,
melting point, glass and decomposition temperatures, density, thermal expansivity, viscosity,
conductivity and ion self-diffusion coefficients. These were compared with those of
non-functionalised (3), as a benchmark salt.[1] A marked difference in thermal stability was
observed between the N- functionalised salts and the non-functionalised (3), the former being up to
170 K less stable than the latter. (1) and (2) also have narrower electrochemical windows than
structural counterparts lacking a tertiary amine function, by about 3 V. The ion self-diffusion
coefficients and conductivities are higher for the open chain (2) than for the cyclic (1) at each
temperature, and the viscosity less. The transport properties are examined using fractional Stokes
Einstein and Nernst Einstein relations and the velocity correlation coefficients (VCC) calculated.
The fractional Stokes Einstein exponents range from (0.95 to 0.98). The Nernst Einstein
equation deviation parameters (!) are such that the mean of the like-ion VCCs is greater than that
for the unlike ions: ! = (0.36 and 0.42) respectively, values typical for ionic liquids. The VCCs are
analysed in terms of the anti-correlated motion of ions, a feature of one-component molten salts,
that contrasts with the correlated motions of ions in electrolyte solutions. According to the VCC
analysis, the distinct diffusion coefficients follow the order D--d < D++d < D+-d, a pattern previously
found for a number of [Tf2N]- salts.
[1] Rther T, Harris K R, Horne M D, Kanakubo M, Rodopoulos T, Veder J-P, Woolf L A , Chem. Europ. J., 2013, 19:
17733 17744.
B22
Structures and Applications of Ionic Plastic Crystals

Based on Fluoroanions
Kazuhiko Matsumotoa,* Ukyo Harinagaa, Ryo Tanakaa, Akira Koyamaa, Rika Hagiwaraa
a
Graduate School of Energy Science, Kyoto University, Kyoto, Japan

*k-matsumoto@energy.kyoto-u.ac.jp
Ionic plastic crytals are observed for some ionic compounds as intermediate phases between
crystal and liquid phases. The constituting ions in ionic plastic cystals are highly disordered and
thus ions can diffuse in ionic plastic crystals, which makes them attractive as solid-state electrolytes.
[1,2,3]
N,N-dimethylpyrrolidinium fluorohydrogenate ([C1C1pyrr][(FH)nF]) give an ionic plastic crystal
phase in a wide n range with the NaCl-type ion configuration [4]. According to pulsed-field
gradient spin-echo NMR, (FH)nF! diffuses as a charge carrier in this phase, giving a high ionic
conductivity (10.3 mS cm!1) as in the case of (FH)nF! based ionic liquids [5,6]. The "Sfus value of
[DMPyr][(FH)2F] is quite low (4.1 J K!1 mol!1) compared to other alkylammonium salts that form
ionic plastic crystals. An electrochemical capacitor using the [DMPyr][(FH)2F] ionic plastic crytsal
was fabricated with activated carbon electrodes to make full use of the high ionic conductivity. The
obtained capacitance behavior is similar to those using fluorohydrogate ionic liquids and show large
capacitance and large voltage dependence of capacitance [7].
Structural analysis of ionic plastic crytals is important to understand the ion conduction
mechanism of ionic plastic crystals as solid state electrolyte. Differential scanning calorimetric
analysis of tetraalkylammonium (Nnnnn+, n = 1-4) and tetraalkylphosphonium (Pnnnn+, n = 1-4) salts
based on BF4! and PF6! shows all of them exhibit one or more solid-solid phase transition. Their
highest temperature solid phases (Phase I) belong to either cubic or hexagonal lattice due to the
highly disordered ions except for some salts ([N1111][BF4], [P1111][BF4], and [P1111][PF6]) which
decompose wihtout melting. Powder and sigle-crystal X-ray diffraction revealed that Phase I of the
present series belong to either CsCl -type, NaCl-type, NaCl -type, NiAs-type, and TBPPF6-type
lattice. The alkyl-chain length and the ratio of the sizes of cation and anion determine the structural
types.
The authors would like to thank Prof. Katsuhiko Tsunashima of Wakayama National College of
Technology for the supply of some phosphonium salts.
References
[1] .M. Pringle, P.C. Howlett, D.R. MacFarlane, M. Forsyth, J. Mater. Chem. 20 (2010) 2056!2062.
[2] D.R. MacFarlane, M. Forsyth, Adv. Mater. 13 (2001) 957966.
[3] L. Jin, K. M. Nairn, C. M. Forsyth, A. J. Seeber , D. R. MacFarlane, P. C. Howlett, M. Forsyth, J. M. Pringle, J. Am.
Chem. Soc., 134 (2012) 96889697
[4] R. Taniki, K. Matsumoto, R. Hagiwara, K. Hachiya, T. Morinaga, T. Sato, J. Phys. Chem. B 117 (2013) 955960.
[5] R. Hagiwara, K. Matsumoto, Y. Nakamori, T. Tsuda, Y. Ito, H. Matsumoto, K. Momota, J. Electrochem. Soc., 150
(2003) D195D199.
[6] K. Matsumoto, R. Hagiwara, Y. Ito, Electrochem. Solid-State Lett., 7 (2004) E41E44.
[7] R. Taniki, K. Matsumoto, T. Nohira, R. Hagiwara, J. Power Sources, 245 (2014) 758763.
B23
Green & sustainable itinerary for O-selective methylation of Hydroxy

acetophenone using phosphonium based ionic liquid
Suresh Jaina* and Ganapati D. Yadavb
a
Manager- Technologist, Reliance Technology Group, Reliance Industries Limited, Mumbai, India
b
Vice Chancellor, Institute of Chemical Technology, Mumbai, India

Email address: suresh.s.jain@ril.com
Abstract:
Green solventless liquid-phase O-methylation of 4-hydroxy acetophenone (4-HAP) with dimethyl
carbonate (DMC) have been studied employing phosphonium based ionic liquid as a catalyst. To
get insight of reaction and design sustainable route for selective methylation of
hydroxyl-acetophenone, various parameters were optimized. DMC was found to be very effective
as a methylating agent and the selectivity for 4-methoxy acetophenone was 100% with complete
conversion of 4-HAP. The detailed kinetic investigation for selective methylation reaction was
performed in high pressure Parr autoclave reactor and reaction found to be pseudo zero order with
respect to 4-HAP. Plausible mechanism for ionic liquid catalyzed reaction was proposed [1, 2]. The
values of apparent activation energy for 2-, 3-, and 4-hydroxyacetophenone are found as 29.0, 27.5,
and 31.0 kcal/mol respectively. The lower catalyst loading, high selectivity for the product of
interest and complete reusability of ionic liquid catalyst makes the process in consonance with the
principles of green chemistry and sustainable process.
CH3
CH3
CH3
Ionic liquid
160 !C
CH3OH
CO2
OCH3
OH
4-HAP
CH3
4-MAP
Dimethyl carbonate
Methanol
Carbon dioxide
Figure 1. Reaction scheme for O-methylation of 4-hydroxy acetophenone

References
[1] Jyothi T.M., Raja T., Talawar M.D., Rao B.S., Appl. Catal. A: Gen., 2001, 211:41-46.
[2] Kirumakki R. S., Nagaraju N., Murthy K.V.V.S.B.S.R., Sankarasubbier N, Appl. Catal. A: Gen., 2002,
226:175-182.
B24
Posters
Biomass Processing of Rice Husks with Partially Hydrated Hydroxides

Ena T. Luis, Benjamin B. Y. Lau, Md. Mokarrom Hossain, William E. S. Hart, Bernadete Cencia-Lay, Jeffrey J. Black,
Trang Q. To and Leigh Aldous*
School of Chemistry, UNSW Australia, Sydney, NSW 2052, Australia
*e-mail address: l.aldous@unsw.edu.au
Rice husks are a major waste product, and are extremely difficult to process due to their high (~20
wt%) silica content. However, if this can be overcome full use of their holocellulose (~60 wt%) and
lignin (~20 wt%) content could be realised in a biorefinery.1 Rice husks can be partially dissolved
in ionic liquids, but require temperatures in excess of 100 C.2,3
Aqueous solutions of tetrabutylphosphonium hydroxide can (at a stretch) be considered as
hydrated ionic liquids. Once the tetrabutylphosphonium hydroxide becomes partially desolvated
this salt-water mixtures can begin to dissolve biomass samples at room temperature but over a
period of months.4
This reliance on rice husks upon their silica armour becomes a weakness that can be exploited by
using partially hydrated tetrabutylphosphonium hydroxide. Despite being predominately water, it
has been demonstrated5 that partially hydrated tetrabutylphosphonium hydroxide can almost
completely dissolve the husk at room temperature, and result in enzymatic glucose yields exceeding
that possible by standard potassium hydroxide and sulphuric acid pre-treatments. The effect of the
water:hydroxide ratio has been investigated, the kinetics of delignification evaluated, and the
solubility of cellulose, lignin and silica.
References:
1. M. M. Hossain and L. Aldous, Aust. J. Chem. 2012, 65, 1465
2. T. N. Ang, L. W. Yoon, K. M. Lee, G. C. Ngoh, A. S. M. Chua and M. G. Lee, Bioresource., 2011,
6, 4790
3. J. G. Lynam, M. T. Reza, V. R. Vasquez and C. J. Coronella, Bioresource Technol., 2012, 114, 629.
4. M. Abe, T. Yamada and H. Ohno, RSC Adv., 2014, 4, 17136
5. E. T. Luis, M. M. Hossain, B. B. Y. Lau, W. E. S. Hart, B. Cencia-Lay, J. J. Black, T. Q. To and
L.Aldous, Submitted
6. 562.
M1
Increasing the efficiency of ionic liquid-based thermoelectrochemical cells

Danah Al-Masria, Maria Forsytha, Douglas MacFarlaneb and Jenny Pringlea
a
The Institute for Frontier Materials, Deakin University, Melbourne, Australia

b
Monash University, Melbourne, Australia

dalmasri@deakin.edu.au
Thermoelectrochemical cells (TECs) are devices capable of converting heat directly into electricity,
promising a future where thermal energy is more widely utilized. 1,2 TECs depend on the Seebeck
effect; when a temperature gradient is applied across the cell, a redox couple within the electrolyte
allows current to flow across the device. The redox potential and temperature gradient are linked by
the Seebeck coefficient, given by
. Recent research efforts aim to increase the efficiency of
TECs by studying different electrode materials, electrolytes and redox couples. The benchmark
value of Seebeck coefficient used today is for an aqueous electrolyte containing the
ferri/ferrocyanide redox couple (
.
As an alternative to this aqueous system, ionic liquids (ILs) are now being investigated as
electrolytes for TECs. Their favourable properties can include thermal stability, allowing high
temperature gradients to be reached and leading to higher potentials and power outputs.3
Furthermore, wide electrochemical windows increase the variety of possible redox couples
available for use, and low vapour pressures enable longer lasting devices.
A cobalt bipyridyl redox couple (Co(bpy)3II/II)) has been shown to produce high Seebeck coefficient
values in previous studies. 4 This is believed to be due to its high reaction entropy, resulting from a
low to high spin transition upon electron transfer. The Seebeck coefficient is directly related to the
reaction entropy by
where n is the number of electrons involved in the reaction and F is
faradays constant.
Here, high Seebeck coefficient values and high TEC power and current outputs are reported for the
Cobalt redox couple in a number of IL-Organic solvent systems. The addition of high boiling point
organic solvents is explored for their role in increasing the solubility of the redox couple, lowering
the viscosity of the ionic liquid and increasing the Seebeck coefficient.
References.
[1] Chum HL, Osteryoung RA. Review of thermally regenerative electrochemical systems. Volume I. Synopsis and
executive summary. In, 1980. p Medium: ED; Size: Pages: 65.
[2] Abraham TJ, MacFarlane DR, Pringle JM. High Seebeck coefficient redox ionic liquid electrolytes for thermal
energy harvesting. Energy & Environmental Science 2013; 6: 2639.
[3] Armand M, Endres F, MacFarlane DR, Ohno H, Scrosati B. Ionic-liquid materials for the electrochemical
challenges of the future. Nature materials 2009; 8: 621-629.
[4] Jiao N, Abraham TJ, MacFarlane DR, Pringle JM. Ionic Liquid Electrolytes for Thermal Energy Harvesting Using a
Cobalt Redox Couple. Journal of the Electrochemical Society 2014; 161: D3061-D3065.
M2
Porous silica spheres-supported Zn-functionalized ionic liquid

as sorbents for CO2 capture
Ian Harvey Arellanoa,c, S. Hadi Madanib, Junhua Huangc and Phillip Pendletona,*
a
Center for Molecular and Materials Sciences, School of Pharmacy and Medical Sciences and Sansom Institute,
University of South Australia, Adelaide, SA 5001, Australia
b
Ian Wark Research Institute, University of South Australia, Mawson Lakes, SA 5095, Australia
c
*phillip.pendleton@unisa.edu.au
Cheaper carbon capture and storage technologies have been under development in recent years as a
way to mitigate the release and proliferation of CO2 to the atmosphere. Supported ionic liquid (IL)
phase materials, where an IL is immobilised on a solid support, are a promising class of sorbents for
CO2 capture,[1] which could be used in fluidized bed technology. They combine the excellent CO2
absorption capacity and selectivity of ILs with the robustness and surface properties of the solid
support. The ionic liquid 1-ethyl-3-methylimidazolium tri[bis(trifluoromethylsulfonyl)imide]
zincate(II) (EZT3) exhibits strong affinity towards CO2.[2] We report the preparation of EZT3
supported by porous silica beads and compare its application for CO2 absorption against
non-supported EZT3.
Silica was deposited on the surface of porous calcium alginate (CaAlg) beads, polymerized to form
a silica network, followed by dissolution of CaAlg. The resulting silica exhibited a bimodal pore
size distribution in the range 5-30 nm. Treatment with an alkaline solution of tetrapropylammonium
ions was found to protect the silica structure from extensive dissolution and to impose a
pore-directing action, forming a unimodal pore network, mean width 10 3 nm, with concomitant
reduction of specific surface area and pore volume. EZT3 deposited on the pore and external
surfaces of the silica beads showed increased thermal resistance compared with the bulk; a positive
effect of confinement[3]. Additionally, the sorption capacity at 313 K, after 600 min exposure to 50
mL/min stream of CO2, for silica with 25% EZT3 loading was 2.12 mmol CO2/g sorbent; bulk
EZT3 absorbed 0.84 mmol/g. Bulk EZT3 exhibits a viscosity-imposed reduction in absorption
rate.[2] Fig. 1 shows silica supported EZT3 had greater capacity for CO2 at any given time compared
with the support and bulk EZT3. Absorption limiting rate analyses for supported EZT3 indicate a
550% increase in initial rate over bulk, and
160% over support.
References
[1] Samanta A, Zhao A, Shimizu GKH, Sarkar P,
Gupta R. Ind. Eng. Chem. Res., 2012, 51,
1438-1463.
[2] Liu H, Huang J, Pendleton P. Energy Procedia,
2011, 4, 59-61.
[3] Chen S, Kobayashi K, Miyata Y, Imazu N, Saito T,
Kitaura R, Shinohara H. J. Am. Chem. Soc., 2009,
131, 14850-56.
Fig. 1. Dynamic CO2 uptake of EZT3, SiO2, and

EZT3-loaded SiO2 beads with EZT3 at 10, 25 and 35
M3
wt%.
Glucose to 5-hydroxymethylfurfural transformation

in acidic aqueous and ionic liquid solvents
Arifina, Maneeporn Puripatb, Vudhichai Parasuk*b,c, Daisuke Yokogawa*a,d, Stephan Irle*a,d
a
Chemistry Department, Graduate School of Science, Nagoya University, Nagoya, Japan

Nanoscience and Technology Program, Graduate School, Chulalongkorn University, Bangkok, Thailand
c
Computational Chemistry Unit Cell (CCUC) Laboratory, Department of Chemistry, Faculty of Science, Chulalongkorn
University, Bangkok, Thailand
d
Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya, Japan
*sirle@chem.nagoya-u.ac.jp
b
Recently, ionic liquids (ILs), such as imidazolium salts, have shown great potential as solvents to
process the biomass into fuels under mild conditions, with less toxicity than volatile organic
solvents. Furthermore, the transformation of hexoses, e.g. glucose and fructose, into
5-hydroxymethylfurfural (HMF) is believed to be one of the key reactions. Many experimental and
theoretical works have been conducted to elucidate
the details of this reaction, but our understanding
of the mechanisms is still far from complete.
Previously proposed mechanisms for glucose
transformation to HMF are shown in Scheme 1.
These mechanisms suggest that the first step of
glucose transformation is the isomerization from
glucose to fructose (1), via cyclic mechanism (A)[1]
Scheme 1. Glucose transformation into HMF;
and open ring mechanism (B)[2], followed by cyclic (A) and open ring mechanism (B)
transformation of fructose to HMF (2). In the
present work, we investigate the reaction pathways
in acidic aqueous and ionic liquid solvents.
RISM-SCF-SEDD[3], a combination of
molecular orbital (MO) theory and statistical
mechanics of molecular liquid, is applied with
density functional theory (DFT) and gold
standard coupled cluster theory CCSD(T).
Temperature and pressure was set to (473.15K, 10
MPa) and (353.15K, 1 atm), for reaction in the
water and IL respectively.
Figure 1 shows the energy profiles of
glucose isomerization to fructose via the open ring Figure 1. Free energy profiles of glucose isomerization
mechanism (1-B). In IL, the free energy profiles of into fructose via open ring mechanism (1-B)
intermediates are lower than in water. Moreover,
the chloride anions from the solvent can stabilize the positively charged molecules, as O4 and O6
become O4 and O6 respectively, by forming covalent bonds in these species. More details will be
given in the poster presentation.
References
[1] Qian X, Wei X., J. Phys. Chem. B, 2012, 116: 10898.
[2] Binder J B, Raines, R T, J. Am. Chem. Soc., 2009, 131: 1979.
[3] Yokogawa D, Sato H, Sakaki S, J. Chem. Phys., 2007, 126: 244504.
M4
Electrodeposition of Pd-Sn Alloy Catalyst from Ionic Liquids for Oxygen

Reduction Reaction
Majid Asnavandi and Chuan Zhao*
School of Chemistry, The University of New South Wales, Sydney 2052, Australia
*Corresponding authors e-mail address: chuan.zhao@unsw.edu.au
Fuel cells have been considered as promising energy storage and conversion devices thanks to their
high energy density, high conversion efficiency and low pollutant emission [1]. Nevertheless, the
sluggish oxygen reduction reaction (ORR) remains one of the problems to be addressed in order to
make fuel cells commercially viable. Pt is the most efficient electrocatalyst for ORR. However, its
high cost and scarcity limit its large-scaled application in fuel cells[2]. It is therefore essential to
search for low cost electrocatalysts with high catalytic activity and long-term operation stability.
Palladium is an alternative electrocatalyst for ORR. Alloying palladium with transition metals not
only improves Pd catalytic properties[3] but also makes it cost effective.
In this presentation, electrochemical behavior of palladium and tin will be studied in protic and
aprotic ionic liquids. Nanostructured palladium-tin alloys will be deposited electrochemically from
ionic liquid electrolytes. The electrocatalytic activity of Pd-Sn alloys towards ORR will be studied
in both acidic and alkaline media. The influence of Pd composition and morphology of deposited
Pd-Sn alloy as well as the synergetic effect of the alloy on ORR will be discussed.
References
[1] Cheng F, Chen J, Chem. Soc. Rev. 2012, 41: 21722192
[2] Morozan A, Jousselme B, Palacin S, Energy Environ. Sci. 2011, 4: 12381254
[3] Suo Y, Zhuang L, Lu J, Angew. Chemi ,2007, 46: 28622864
M5
Bioethanol production from lignocellulose materials via the combined use of

ionic liquids and enzymes.
San Mei Bong a*, and Nolene Byrne a
a
Institute for Frontier Materials, Deakin University, Pigdons Road, Waurn Ponds, Victoria, Australia, 3217.
E-mail: sbong@deakin.edu.au
New technologies aimed at improving the bioethanol production from lignocellulosic materials is
critically needed. Currently the use of enzymes offers significant advantages over traditional acid
catalysed methods. However, improvements in enzyme activity and the need to pre-treat the
lignocellulosic material limit this technology. Here we are exploring the use of ionic liquids to
enhance the thermostability and activity of cellulose enzymes. We have characterized the activity of
the enzyme in the presence of various ionic liquids as well as the impact these ionic liquids have as
potential pre treatment solvents thus eliminating the need to extensive rinsing and removal of the IL
during the conversion process.
M6
Compartmentalisation by Vesicles in Ionic Liquids

Saffron J. Bryanta, Rob Atkinb, Gregory G. Warra*
a
b
School of Chemistry F11, The University of Sydney, NSW 2006, Australia
Priority Research Centre for Advanced Particle Processing and Transport,

Compartmentalisation is one of the features of prebiotic environments believed to be essential to the

origin of life. To date investigations of prebiotic environments have understandably focused on the
self-assembly of compartments like micelles and vesicles in aqueous systems. However, the
possibility of self-assembling systems developing in non-aqueous solutions such as ionic liquids is a
largely unexplored area that may yield new insights into the postulated uniqueness of water, or form
the basis of truly alien forms of life. Preliminary investigations have demonstrated that some lipids
self-assemble into swellable lamellar structures in a range of protic ionic liquids (PILs), as they do
in water. These lipids also exhibit a gel-to-lamellar phase (L! ! L") transition on warming, and
vesicle budding from myelenic figures.
Differential scanning calorimetry experiments have demonstrated that ionic liquid solvents alter the
main transition temperature of lipids. Several publications suggest that this is a result of the ionic
liquid ions shielding electrostatic repulsions between phospholipid head-groups[1]. However, results
to date suggest that there are other factors at work, as changing cation structure results in a different
transition temperature. Further investigation into these factors is currently being carried out.
We have shown by dynamic light scattering and small-angle X-ray and neutron scattering that some
of these lipids can also be assembled into unilamellar vesicle dispersions in various PILs as a model
for protocell formation. This raises the possibility of water-free, synthetic life-forms, which would
also significantly broaden the prospective temperature range of the goldilocks zone of planetary
orbits which could potentially support life. Bilayer thicknesses of egg phosphatidylcholine vesicles,
for example, are very similar in ethylammonium nitrate and water, but bilayer thickness and fluidity
in phospholipids are sensitive to chain length and saturation, and also to PIL structure.
References
[1] Grillo I, Kats EI, Muratov AR, Langmuir., 2003, 19: 4573-4581
M7
The effect of ionic liquids on reactions at phosphorus

a
Bradley J. Butlera and Jason B. Harper

School of Chemistry, University of New South Wales, Sydney, New South Wales, Australia
While reactions at carbon centres in ionic liquids have been studied extensively,[18] the equivalent
for phosphorus centres is currently lacking. Such molecules are of particular interest not only for
their roles in fields such as pesticides, but also due to their reported stability in ionic liquids.[911]
The reaction being investigated is the nucleophilic attack of ethanol on diethyl chlorophosphate
(DCP) (Scheme 1) in one of a range of ionic liquids (Figure 1). Initial studies focused on investigating
the effect of changing the solvent system on the second order rate constant of this reaction,
particularly the changing the proportion of the ionic liquid and the structure of the cation.
Scheme 1: The reaction of d6-ethanol with diethyl chlorophosphate.
Figure 1: The ionic liquids used in this project a) [bmim][Tf2N] b) [bm4im][Tf2N] c) [bmpyr][Tf2N] d) [TOA][Tf2N] e) [bpyr][Tf2N]
The enthanolysis of DCP was followed via 1H NMR spectroscopy in a range of ionic liquids
ranging from !IL 0 to 0.80 as exemplified in Figure 2a. It is important to note that the pattern
observed was atypical when compared to previous studies at carbon centres.[5]
Temperature-dependent studies followed in order to provide activation parameters at !IL 0, 0.7 and
the concentration providing the greatest rate constant (Figure 2b). From these activation parameters
it was found that the rate constant enhancement seen was a result of an enthalpic benefit
overcoming a corresponding entropic cost.
a)
b)
Figure 2: a) The effect of the mole fraction of the ionic liquid [BMIM][Tf2N] on the second order rate constant for the reaction in
Scheme 1 with co-solvent d6-ethanol. b) Eyring plot at three mole fractions of [BMIM][Tf2N] ("=0, !=0.3, #=0.7) for the reaction
in Scheme 1 with co-solvent d6-ethanol.
[1] H. M. Yau, S. J. Chan, S. R. D. George, J. M. Hook, A. K. Croft, J. B. Harper, Molecules 2009, 14, 252134.
[2] H. M. Yau, A. G. Howe, J. M. Hook, A. K. Croft, J. B. Harper, Org. Biomol. Chem. 2009, 7, 35725.
[3] S. G. Jones, H. M. Yau, E. Davies, J. M. Hook, T. G. A. Youngs, J. B. Harper, A. K. Croft, Phys. Chem. Chem.
Phys. 2010, 12, 18738.
[4] E. E. L. Tanner, H. M. Yau, R. R. Hawker, A. K. Croft, J. B. Harper, Org. Biomol. Chem. 2013, 11, 61705.
[5] S. T. Keaveney, J. B. Harper, RSC Adv. 2013, 3, 15698.
[6]H. M. Yau, S. T. Keaveney, B. J. Butler, E. E. L. Tanner, M. S. Guerry, S. R. D. George, M. H. Dunn, A. K. Croft, J.
B. Harper, Pure Appl. Chem. 2013, 85, 19791990.
[7] B. Y. W. Man, J. M. Hook, J. B. Harper, Tetrahedron Lett. 2005, 46, 76417645.
[8] H. M. Yau, A. K. Croft, J. B. Harper, Faraday Discuss. 2012, 154, 365.
[9] E. J. Amigues, C. Hardacre, G. Keane, M. E. Migaud, Green Chem. 2008, 10, 660.
[10] E. J. Amigues, C. Hardacre, G. Keane, M. E. Migaud, S. E. Norman, W. R. Pitner, Green Chem. 2009, 11, 1391.
[11] E. J. Amigues, C. Hardacre, G. Keane, M. E. Migaud, M. ONeill, Chem. Commun. 2006, 724.
M8
Electrochemistry of ionic liquids for redox flow battery electrolytes

Diogo Cabrala, Xinyi Zhanga, Douglas MacFarlanea,*
a
School of Chemistry, Monash University, Melbourne, Australia

*douglas.macfarlane@monash.edu
Redox flow batteries (RFB) are an emerging technology in which the electrolytes are stored in tanks
outside of the batterys electrode compartment. That gives the RFB the unique characteristic of
separating the energy and power capacities, allowing different battery designs for each application.
In the context of sustainable energy storage applications, this allows the construction of very high
energy capacity batteries. However, RFBs normally have low energy density, which limits their
application[1]. The use of a non-aqueous electrolyte, with wider electrochemical window, would
enable the development of RFBs with higher energy density. However, organic solvents
traditionally used in electrochemical devices, as alternative to aqueous electrolytes, have safety
concerns, due to their flammability, toxicity and volatility. Ionic liquids (ILs) are a next-generation
electrolyte material for electrochemical devices that have high stability, electrical conductivity and
large electrochemical window [2]. The luxury to choose their constituent ions provides an ability to
design ILs that maintain their advantageous electrochemical properties, while removing problems
of toxicity and flammability. A disadvantage of using ILs is its high viscosity, which is a source of
energy inefficiency due to the power required to pump viscous liquids[3]. However, a new design for
RFBs using electrolytes with high viscosity was recently proposed[4], enhancing the possibility of
developing a RFB using ILs as electrolytes. In this work, we present characterisation and
electrochemical studies on ionic liquids for use as electrolytes in redox flow batteries.
References
[1] Wang W, Luo Q, Li B, X. Wei X, Li L, Yang Z. Adv Funct Mat,2013, 23:970-986.
[2] Chakrabarti M, Mjalli F, AlNashef I, Hashim M, Hussain M, Bahadori L,Low C. Renew Sust Energ Rev, 2014,
30:254-270.
[3] Katayama Y, Konishiike I, Miura T, Kishi T, J Power Sources, 2002:327-332.
[4] Smith K, Chiang Y-M, Carter W, J Electrochem Soc, 2014, 161:A486-A496.
M9
Ordered Nanoporous Metals from Ionic Liquid Templates for

Sustainable Energy Applications
Kun Chena, Xinyi Zhang a, Douglas R. MacFarlanea*
a
School of Chemistry, Monash University,3800 Clayton, Australia

*E-mail:douglas.macfarlane@monash.edu
The ever-increasing energy consumption, limited nature of fossil fuels, and rising public awareness
for environmental protection has resulted in research focusing on devices such as fuel cells to
provide clean and renewable energy. Fuel cells require catalysts to operate efficiently, and currently
use very expensive platinum catalysts.[1] [2] In order to reduce the cost of the catalyst and improve
the economic viability of fuel cells, our research aims to reduce the mass of platinum per surface
area of the catalyst. We will address this using two strategies; we aim to control the size and shape
of the deposited structures,[3] and investigate new, cheaper elements for catalytic activity (such as
ruthenium[4]). One-dimensional metallic nanostructures, particularly those composed of noble
metals, have sparked great scientific interest for practical applications, owing to their uniquely
anisotropic structure.[5]Among those 1D nanostructures, metal nanotubes possess more advantages,
such as high specific surface area and high accessibility of guest species, derived from their inherent
hollow space. However In almost all the nanotubes that have been synthesized, the ordering of
mesoporous structures was relatively low and the ordered domain size was quite small. This work
seeks to synthesise nanotube with tailored mesostructures by a templating approach where the
template is derived from ionic liquid species.
[1] A. Kloke, F. von Stetten, R. Zengerle, S. Kerzenmacher, Advanced Materials 2011, 23,
4976-5008.
[2] J. Larminie, A. Dicks, M. S. McDonald, Fuel cell systems explained, Vol. 2, Wiley New York,
2003.
[3] X. Zhang, W. Lu, J. Dai, L. Webley, Angewandte Chemie International Edition 2010, 49,
10101-10105.
[4] Y.-C. Liang, Y.-W. Juan, K.-T. Lu, U.-S. Jeng, The Journal of Physical Chemistry C 2012, 116,
26649-26655.
[5] C. Koenigsmann, E. Sutter, T. A. Chiesa, R. R. Adzic, S. S. Wong, Nano letters 2012, 12,
2013-2020.
M10
Structure of PEO-PEGE Block Polyethers in Ethylammonium Nitrate and

Adsorbed to Silica
Zhengfei Chen,a Kazuhide Ueno,b Paul Fitzgerald,c Masayoshi Watanabe,b Greg Warr,c Rob Atkin,a*
a
b

We have investigated the self-assembly of diblock polyethers consisting of hydrophilic PEO and a
hydrophobic poly(ethyl glycidyl ether) (PEGE) blocks in EAN. PEGE has a better compatibility
(miscibility) with hydrophillic ionic liquids (ILs) compared to PPO due to its higher oxygen weight
fraction,[1] but is less miscible than PEO. The difference in the miscibility of the PEO and PEGE
segments leads to micellisation of the PEO-PEGE polyethers in aprotic ILs[2] and water[3]. In this
work we explore bulk (micelles and liquid crystals) and surface structures formed in protic ionic
liquids by four PEO-PEGE polyethers (Table 1) with various block sizes to elucidate the effect of
changing the block length on self-assembled structure. Small angle neutron scattering and dynamic
light scattering has been used to probe the structure of the micelles, small angle x-ray scattering and
polarising optical microscopy has been used to study liquid crystals (Figure 1), and atomic force
microscope force curves and images (c.f. Figure 2 below) has been used to study the structure of
polymer aggregates at the silica EAN interface.
!!!Table 1 Polyethers with various fraction of PEO

total
EGE136
EGE109EO54
EGE113EO115
EGE104EO178
Mn
14008
13629
16725
18581
fEO
0
0.155
0.274
0.388
Hexagonal
!"!#$%!&#'(
EAN
Figure 1. Hexagonal liquid crystals

formed by "#"$%&"'$() in EAN
viewed under a polarising optical
microscope.
Figure 2. AFM image of "#"$%&"'$()

micelles (1 wt%) adsorbed at the
EAN-silica interface.
References
[1]
[2]
[3]
K. Kodama, R. Tsuda, K. Niitsuma, T. Tamura, T. Ueki, H. Kokubo, M. Watanabe, Polym. J. (Tokyo, Jpn.)
2011, 43, 242-248.
T. Ueki, M. Watanabe, T. P. Lodge, Macromolecules 2009, 42, 1315-1320.
M. Ogura, H. Tokuda, S. I. Imabayashi, M. Watanabe, Langmuir 2007, 23, 9429-9434.
M11
Novel Multifunctional Organic Salts to Combat Microbiologically Influenced

Corrosion
Alison Chonga*, Marianne Seter b, Melanie J. Thompson c, Douglas R. MacFarlane a, Maria Forsythb
a
School of Chemistry, Monash University, Clayton, Australia

Institute for Frontier Materials, Deakin University, Burwood, Australia
c
School of Medicine, Deakin University, Geelong, Australia
*alison.chong@monash.edu
Biofilm formation and resulting microbiologically influenced corrosion (MIC) is a problem in a

wide range of fields, affecting both marine infrastructure and medical implants, and causing billions
of dollars worth of damage every year. This work presents dual-active salts that have shown
multifunctional inhibitory effects when employed to protect an exposed steel surface.[1] A synthetic
strategy was followed whereby known biocidally active or corrosion inhibiting ions are combined
to make novel salt and ionic liquid formulations. As well as preventing MIC in the presence of
relevant marine bacteria, some of these novel salts have been shown through electrochemical testing
and spectroscopic imaging to act as inhibitors against general corrosion. These materials have
potential to be commercially implemented as a component of a protective antimicrobial surface
coating.
References
[1] Seter M, Thomson M J, Chong A, MacFarlane D R, Forsyth M, Aust. J. Chem, 2013, 66:921-929.
M12
A low concentration of ionic liquid dissolved in base oil lubricates as effectively

as the pure ionic liquid
Hua Li,a Peter K. Cooper,a Anthony E. Somers,b Mark W. Rutland,c Patrick C. Howlett, b Maria Forsyth b and Rob
Atkina,*
a
Centre for Advanced Particle Processing and Transport, The University of Newcastle, Callaghan, NSW 2308,
Australia.
b
Institute for Frontier Materials, Deakin University, 221 Burwood Highway, Burwood, Victoria 3125, Australia.
c
School of Chemistry, KTH Royal Institute of Technology, SE 100 44 Stockholm Sweden.
One of the challenges for using ILs as lubricants is their high cost. However, many IL ions have
surfactant-like structures, which suggests their use as additives to a lubricating base oil; when
diluted in this way the IL is much more cost effective. In this article we show that, at the nanoscale,
a 1 mol% solution of IL in oil has comparable tribological performance to the pure IL, c.f. Figure1.
Higher IL concentrations only marginally increase performance. Atomic force microscopy (AFM)
nanotribology measurements reveal that a 1 mol% solution of ionic liquid (IL) dissolved in an oil
lubricates the silica surface as effectively as the pure IL. The adsorption isotherm shows that the IL
surface excess need only be approximately half of the saturation value to prevent surface contact,
and effectively lubricate the sliding surfaces.
(##
Lateral Force (nN)
160
> ?+
140
/ 5 6, +5 3-7 2+8 , -9:; <
"##
'##
120
@ 8 65 :,
100
80
60
40
150
200
250
300
Normal Load (nN)
# 0# $ -1 234 -./
# 0# " -1 234 -./
# 0$ -1 234 -./
350
&##
# 0" -1 234 -./

$ -1 234 -./
% -1 23-4 -./
" -1 23-4 -./
$ # -1 234 -./
) *+, -./
%##
$##
#
!"#
"#
$##
$"#
%##
%"#
&##
&"#
'##
'"#
"##
; 2+1 5 3-/ 25 =-9:; <
Figure 1. Lateral force versus normal load in air and IL octane solutions for a sharp silicon AFM tip (r = 5 nm) sliding
on a silica surface over 100 nm at 6 m s-1. The inset shows lateral force versus normal load for IL concentrations of 1
mol% and above at higher normal load regimes.
M13
Chlorophyll extraction from spinach using aqueous solutions of ionic liquids

Ana M. Ferreiraa, Ana Cludia Leitea, Imran Khana, Mara G. Freirea and Joo A. P. Coutinhoa,*
a
Chemistry Department, CICECO, University of Aveiro, Aveiro, Portugal

*jcoutinho @ua.pt
Chlorophyll a and b are natural pigments found in green plants. Furthermore, chlorophyll display
interesting properties such as protective features against toxins, or the ability to minimize some
drug side effects in humans. Due to these valued properties, chlorophylls are currently used by the
food, pharmaceutical and cosmetic industries[1]. However, chlorophylls a and b extracted from
natural sources are quite expensive. In fact, the classical methods to extract chlorophylls from
biomass have low efficiency yields and produce compounds with low purity. The organic
compounds commonly employed are volatile, toxic and flammable leading to several risks and a
poor environmental performance. In this context, the use of ionic liquids (ILs) as alternative
solvents can be foreseen as a promising approach, due to their intrinsic characteristics, and an
enhanced solvation ability for target biomolecules.
The aim of this work is to use aqueous solutions of ILs to extract chlorophylls from spinach leaves
envisaging the development of a greener cost-effective technology. We and others[2,3] have
previously shown that ILs and their mixtures with water or organic solvents display a high
capability to extract valuable chemical compounds from biomass. To improve the extraction yields
and purification factors several operational parameters (IL concentration, contact time, solidliquid
ratio and temperature of extraction) were investigated. For that purpose, a surface response
methodology was employed. The recovery of chlorophylls, and the reusability and recyclability of
the IL solutions were also investigated.
Acknowledgments: This work was financed by national funding through the projects EXPL/QEQ-PRS/0224/2013 and
PEst-C/CTM/LA0011/2013. A. M. Ferreira acknowledges FCT for the PhD grant SFRH/BD/92200/2013.
References:
[1] M. Hojnik, M. !kerget, and ". Knez, Sep. Purif. Techn., 2007, 57: 37-46.
[2] A. F. M. Cludio, A. M. Ferreira, M. G. Freire and J. A. P. Coutinho, Green Chem., 2013, 15: 2002-2010.
[3] K. Bica, P. Gaertner, and R. D. Rogers, Green Chem., 2011, 13:1997-1999.
M14
Polarity control of aqueous biphasic systems using ionic liquid mixtures

Helena Passosa, Teresa B. V. Dinisa, Mara G. Freirea, Joo A.P. Coutinhoa,*
a
Chemistry Department, CICECO, University of Aveiro, 3810-193 Aveiro, Portugal

*jcoutinho@ua.pt
Aqueous biphasic systems (ABS) are liquid-liquid separation processes that consist in two
immiscible aqueous-rich phases and can be created by the mixture of two polymers, a polymer with
a salt or two salts. Due to the aqueous nature of the phases ABS are ideal media for the separation
of biomolecules. The identification of ionic liquids (ILs) as ABS forming compounds created a
range of novel separation systems with additional advantages when compared to polymer-based
ABS, such as low viscosity, quick phase separation and high extraction efficiency.
Phase diagrams of ternary systems composed of ILs, salts and water are widely studied and reported
on literature.[1] It is also well known that the polarity of the coexisting phases of the ABS is
essentially dependent of the IL anion.[1] In the present work it was studied the possibility of
manipulating the polarities of the ABS phases through the mixture of two ILs with very distinct
polarities in different molar proportions the [C4mim][CF3SO3] and [C4mim]Cl. With this aim,
novel phase diagrams of ABS constituted by a mixture of [C4C1im]Cl and [C4C1im][CF3SO3] in
different molar proportions, K2CO3 and water were characterized. Moreover, the relative
hydrophobicity of the equilibrium phases were quantified through the partition coefficients of a
series of dinitrophenylated (DNP) amino acids. The results obtained were compared with the
relative polarities of simple ABS composed of imidazollium-based ILs, K2CO3 and water.
Acknowledgments: This work was financed by national funding from Fundao da Ciencia e
Tecnologia
FCT,
through
the
projects
PTDC/QUI-QUI/121520/2010
and
Pest-C/CTM/LA0011/2013. The authors also acknowledge FCT for the PhD grant
SFRH/BD/85248/2012 of H. Passos.
References
[1] M. G. Freire, A. F. M. Cludio, J. M. M. Arajo, J. A. P. Coutinho, I. M. Marrucho, J. N. Canongia Lopes and L. P.
N. Rebelo, Chem. Soc. Rev., 2012, 53: 140-143.
M15
Swelling of the Near-Surface Nanostructure of Propylammonium Nitrate by

Octanol Imaged Using Amplitude-Modulated Atomic Force Microscopy
Samuel Cronshawa, Aaron Elbournea, Kislon Voitchovskyb, Gregory G. Warrc, Rob Atkina,*
a
Discipline of Chemistry, The University of Newcastle, NSW 2308, Callaghan, Australia

b
Department of Physics, Durham University, Durham, England, United Kingdom.
c
School of Chemistry, The University of Sydney, NSW 2006, Australia
* rob.atkin@newcastle.edu.au
Amplitude modulated (AM) - atomic force microscopy (AFM) has been used to elucidate the
near-surface nanostructure of mixtures of an ionic liquid, propylammonium nitrate (PAN), and
octanol at the mica interface. Pure PAN posseses a sponge-like bulk liquid nanostructure resulting
from solvophobicity; the cation alkyl chain and charged groups segregate into apolar and polar
domains, respectively. The presence of the mica surface flattens the sponge-like nanostructure into
layers near the interface. The near-surface structure of the PAN/octanol (vol/vol% - 10, 30,
50%)-mica systems have been imaged with high resolution. Similar to PAN, octanol has both
apolar (C8 alkyl chain) and polar (alcohol group) moeities. When dissolved in PAN the alcohol
group of octanol is solvated by the polar doamin of PAN whilst the alkyl chain is solvated by the
apolar region. Hence, the solvated octanol molecules swell the nanostructure of PAN, especially the
apolar domains. Swelling increases with octanol concentration, c.f. Figure 1.
Figure 1. Topographic AM-AFM image of the PAN-Octanol nearsurface structure at the mica
interface. (A) Pure PAN (B) 10% Octanol:PAN (C) 30% Octanol:PAN (D) 50% Octanol:PAN
M16
Use of ionic liquids for the separation of polyester/cotton textile wastes: A

complete recycling solution
Rasike De Silva a*, Xungai Wang a and Nolene Byrne a
a
Institute for Frontier Materials, Deakin University, Pigdons Road, Waurn Ponds, Victoria, Australia, 3217.
E-mail: rdesil@deakin.edu.au
Improving the recycling of textiles has become an issue for the 21st century. Annually
approxiamtely 1 trillion tons of textile waste is discarded to Australian landfill[1]. The recylcing of
textiles is complicated by the issue that he majority of textile products are blended materials. For
example the majoiroty of clothing is manufactured from a polyester/cotton yarn[2]. Seperation of
polyester and cotton into its individual components is difficult; mechanical seperation is not
possible and chemical seperation requires harsh processing paramters[2, 3]. We report a new
environmentally friendly and convinient approach to seperate and subsequentialy utilise
polyester/cotton blends using ionic liquids (ILs). We have selected cellulose dissolving
1-allyl-3-methylimidazolium chloride (AMIMCl)[4, 5]. The polyester/cotton blend can be seperated
by selectively dissolving the cotton component, with the benefit that the IL can be recycled and
reused[5]. The polyester; a non renewable petrolium resource was recovered in high yield of more
than 98% and posses the same melting temperature as pure polyester. This is important in melting
the polyester to produce recycled polyester products. The cotton was regenerated by coagulation
using water into either films or wetspun in fibres.
Figure 3: Seperation and utilisation of textile blend wastes

References
[1]
[2]
[3]
[4]
[5]
(2010, 18 March 2014). TTNA aims to recycle fibre waste from landfills. Available:
http://www.fibre2fashion.com/news/textile-news/australia/newsdetails.aspx?news_id=86427
Zou Y, Reddy N, and Yang Y, "Reusing polyester/cotton blend fabrics for composites," Composites Part B:
Engineering, 2011, 42: 763-770.
Negulescu I, Kwon H, Collier B J, Collier J R, and Pendse A, "Recycling cotton from cotton/polyester
fabrics.," Text Chemistry Color, 1998, 30: 31-35.
Cao Y, Wu J, Zhang J, Li H, Zhang Y, and He J, "Room temperature ionic liquids (RTILs): A new and
versatile platform for cellulose processing and derivatization," Chemical Engineering Journal, 2009, 147:
13-21.
De Silva R, Wang X, and Byrne N, "Tri-component bio-composite materials prepared using an eco-friendly
processing route," Cellulose, 2013, 20: 2461-2468.
M17
H-bond capacity and self-assembly of cationic surfactants in protic ionic liquids

Andrew Dolana, Rob Atkinb, Gregory G. Warra,*
a

*Gregory.Warr@Sydney.edu.au
Surfactant self-assembly can occur in only a small number of molecular solvents (most commonly
water), however recently it has been found to occur in many ionic liquids. Using ionic liquids offers
a unique way to examine this behaviour, as it is possible to alter intermolecular interactions through
systematic structural changes in the solvent or surfactant, and observe their effects on the
self-assembled molecules. At present there is a substantial volume of work concerning surfactant
self-assembly in protic ionic liquids (PILs),[1] however few studies have made systematic changes
in either surfactant[2] or ionic liquid. In this study we have examined micelle and liquid crystal
formation of a series of cationic surfactants (from primary to quaternary ammoniums) in some PILs,
in order to elucidate the effect of changing the hydrogen-bonding capacity of the surfactant head
group.
Micelle formation and structure of dodecyl-, dodecylmethyl-, dodecyldimethyl-, and
dodecyltrimethyl-ammonium nitrate and thiocyanate salts was examined in their common anion
PILs, ethylammonium, propylammonium and ethanolammonium nitrate (EAN, PAN and ETAN),
and thiocyanate (EASCN and ETASCN) using small-angle x-ray and neutron scattering (SAXS and
SANS). Lyotropic liquid crystal formation was also examined by a combination of polarising
optical microscopy and SAXS.
While nitrate surfactants in nitrate PILs formed micellar solutions, their critical micelle
concentrations and micelle morphology, as well as the type and number of lyotropic phases was
sensitive to the head group structure and H-bonding capacity. The thiocyanate surfactants in
EASCN behaved similarly to the nitrates, but in ETASCN behaved very differently. In the
concentration and temperature range studied only dodecyltrimethylammonium thiocyanate was
fully soluble in ETASCN and formed well defined micelles. Both micelle and liquid crystal
structures in these PILs are compared with corresponding aqueous systems, and the effects of
surfactant anion on self-assembly in PIL and aqueous solvents explored.
References
[1] Greaves T. L., Drummond C. J., Chem. Soc. Rev., 2008, 37:1709-1726
[2] Araos M. U., Warr G. G., Langmuir, 2008, 24:9354-9360
M18
The directed formation of high-order polybromides from ionic liquids

Max E Eastona, Antony J Warda, Anthony F Mastersa, Thomas Maschmeyera*
a
Laboratory of Advanced Catalysis for Sustainability, School of Chemistry F11, University of Sydney, 2006,
AUSTRALIA
Polybromides can play important roles across diverse areas, including carbon nanotube
modification, battery technologyand synthetic chemistry.[1-3] However, our understanding of the
factors that control polybromide formation is still significantly less well developed than it is for the
heavier, less volatile polyiodides.[4] Ionic liquids have been proposed as an ideal synthetic media for
high-order polybromides due to their ability to suppress the bromine vapour pressure and provide a
wide liquidus range.[5] Nonetheless, controlled design of polybromide structures has rarely been
attempted, often ignoring the templating and stabilising effect of the ionic system at play.
We present in the first instance, an outline of a first-principles approach to understanding the factors
that influence the efficacy of polybromide formation from bromide salts of common ionic liquids.
Based on these insights, we describe the preparation of a series of polybromide monoanions (from
penta- to undecabromide) in a room-temperature ionic liquid system (tetrabutylphosphonium
bromide ([P4,4,4,4]Br) in trihexyltetradecylphosphonium bis(trifluoromethanesulfonimide)
([P6,6,6,14]NTF2), and the resulting isolation of the largest reported polybromide species to date:
[P4,4,4,4]2[Br24] (see Fig. 1).
(+
!"#$%&'()'!"#$%&'()* $,-./0'-123#$32452-5$,'#,4'#3$6'-1$45$7!89$:/:;#1'
References
1.
2.
3.
4.
5.
Sung, D., et al., App. Phys. Lett., 2007. 90(9):093502

Singh, P. and B. Jonshagen, J. Power Sources, 1991. 35(4): 405-410.
Ruasse, M.F., et al., J. Am. Chem. Soc., 1997. 119(51):12492-12502.
Svensson, P.H. and L. Kloo, Chem. Rev., 2003. 103(5): 1649-1684.
Wolff, M., A. Okrut, and C. Feldmann, Inorg. Chem., 2011. 50(22): 11683-11694.
M19
Nanostructure of Ionic Liquid-Solid Interfaces Revealed with High Resolution

Using Amplitude Modulated-Atomic Force Microscopy
Aaron Elbournea, Kislon Voitchovskyb, Gregory G. Warrc, Rob Atkina .*
a
Discipline of Chemistry, The University of Newcastle, NSW 2308, Callaghan, Australia.

b
Department of Physics, Durham University, Durham, England, United Kingdom.
c
School of Chemistry, The University of Sydney, NSW 2006, Australia.
*Rob.Atkin@uon.edu.au
Amplitude Modulation Atomic Force Microscopy (AM-AFM) has been used to resolve the
structure of Ionic Liquids (IL) at the mica and graphite interface with high resolution. The ILs
investigated are propylammonium nitrate (PAN) and dimethylethylammonium formate (DMEAF).
Images of the IL ions in direct contact with, and near to, the surface have been obtained with
unprecedented clarity; the lateral structure is much more pronounced than previously suspected.
These results will impact upon a wide range of fields where surface - IL interactions play a role,
which include charge storage devices, electrodeposition, dye solar cells, and lubrication, amongst
others, because the physical arrangement of IL ions at the interface determines process efficiency.
Figure 1. (A) Topographic AFM image of the PAN-mica interfacial innermost surface structure. The inset shows
the 2D fast Fourier transform (B) Topographic AFM image of the near surface structure of the PAN-mica interface
(C) Amplitude & phase vs. distance profile of the PAN-mica system normal to the interface. Distinct maxima have
been marked in both the phase and amplitude data ~0.6 nm apart in agreement with the molecular dimension of
PAN. (D) Section analysis taken across the line in Figure 1(B) showing the height of the near surface structure
which is
~ 2 nm.
M20
Electrochemical Preparation of Nanoporous poly (3,4-ethylenedioxythiophene)

on carbon substrate electrodes from ionic liquid for supercapacitors
Wei-Cheng Fua, Chung-Jui Sua, Po-Yu Chenb and I-Wen Suna*
a
National Cheng Kung University Department of Chemistry, Tainan, 701 Taiwan
b
Department of Medicinal and Applied Chemistry; Center of Excellence for Environmental Medicine, Kaohsiung
Medical University, Kaohsiung City 807, Taiwan
*E-mail address:iwsun@mail.ncku.edu.tw
Abstract
Nanoporous poly(3,4-ethylenedioxythiophene) (PEDOT) electrodes for supercapacitor applications
were prepared on carbon paper and graphite paper, respectively. A layer of poly(styrene) (PS)
template was first self-assembled onto the carbon or graphite substrates. The PEDOT was then
electroploymerized in the interstitial spaces of the PS coated substrate from the
1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([BMI][TFSI]) ionic liquid using
current pulse technique.[1] Porous PEDOT electrode was obtained after removal of the PS template
with toluene.[2] The nanoporous structures were characterized by scanning electron microscopy
(SEM). The electrochemical performance of the nanoporous PEDOT film was investigated in
different electrolyte, including 1-butyl-3-methylimidazolium diacyanamide ([BMI][DCA]),
[BMI][TFSI], 1-butyl-3-methylimidazolium tetrafluoroborate ([BMI][BF4]) ionic liquids, and 0.1M
KClO4 aqueous bath. Cyclic voltammetry was used to characterize the specific capacitance at
various scan rates. The nanoporous PEDOT electrodes exhibit larger specific surface area than the
PEDOT electrodes without using PS template; it also increases the specific capacitance larger.
References
[1] Pandey G. P., Rastogi A. C., Electrochimica Acta, 2013, 87, 158-168.
[2] Santos L., Martin P., Ghilane J., Lacaze P.-C., Randriamahazaka H., Abrantes L. M., Lacroix, J.-C.,
Electrochemistry Communications, 2010, 12 (7), 872-875.
M21
The effective charge of the cations and anions in EMIMFSA ionic liquid studied
by eNMR
Batchimeg Ganbold, Gang Zheng, Gary R. Dennis, William S. Price1*
Nanoscale Organisation and Dynamics Group, University of Western Sydney, Penrith, NSW, 2751, Australia.
The usage of ionic liquids (ILs) as electrolytes in modern high performance batteries requires an
understanding of the charge transfer mechanisms in the electrolytes. Interestingly, despite their
wide usage and enormous potential, the effective charge distribution of ILs is poorly understood.
The electrophoretic mobility () and charge distribution (ze) of the cations and anions in ILs have
been studied computationally, but have not been widely studied using the electrophoretic Nuclear
Magnetic Resonance (eNMR) technique [1,2]. eNMR is a combination of electrophoresis with a
pulsed gradient spin-echo (PGSE) NMR diffusion measurement [3] and provides information on the
electrophoretic mobility and effective charge distribution of ILs. In this study the electrophoretic
mobility and self-diffusion of the cation and anion of the ionic liquid 1-ethyl-3-methylimidazolium
bis(fluorosulfonyl)imide (EMIMFSA) were measured with eNMR at 298 K. The charges of the
cation and anion of EMIMFSA were calculated from the experimentally obtained electrophoretic
mobility and self-diffusion coefficients of the cation and anion, as 0.79 0.01 e and 0.45 0.03 e,
respectively.
Schmidt et al. determined the effective charges of the cation and anion in 1,
3-dimethylimidazolium chloride IL, as 0.63 e with molecular dynamics simulations [2]. In a
computational study Rigby and Izgorodina determined the cation charge to be between 0.55 and 0.7
e which is in agreement with our measurements [4].
Structure of the IL investigated in this work:
H (4)
(5) H
O
H3C
O
N
CH3
C
H2
H (2)
EMIM cation
FSA anion
References
[1] K. Hayamizu, S. Seki, H. Miyashiro, Y. Kobayashi, J Phys Chem B Lett 110 (2006) 22302.
[2] J. Schmidt, C. Krekeler, F. Dommert, Y. Zhao, R. Berger, L.D. Site, C. Holm, J Phys Chem B 114 (2010) 6150.
[3] E. Pettersson, I. Fur, P. Stilbs, Concepts Magn Reson Part A 22 (2004) 61.
[4] J. Rigby, E. I. Izgorodina, Phys Chem Chem Phys. 15 (2013) 1632.
M22
Isothermal vapor-liquid equilibria for ternary mixtures of toluene and heptane

with pure and mixed ionic liquids involved in the aromatic extraction
Pablo Navarro, Marcos Larriba, Julin Garca*, and Francisco Rodrguez
Complutense University of Madrid, 28040 Madrid, Spain
*jgarcia@quim.ucm.es
The use of ionic liquids (ILs) as solvents in the liquid-liquid extraction of aromatics from their
mixtures with aliphatics has been one of the most relevant research fields in the last years. The
negligible vapor pressure of ILs and the good performance achieved using ILs as extraction solvents
have been the reasons for considering IL-based solvents as good candidates in order to replace
conventional organic solvents. The use of pure ILs instead of now-used solvents as sulfolane would
imply an important reduction in both operational and capital investment costs, mainly because of
the reduction in heating and purification steps[1]. Recently, the use of binary mixtures of ILs has
also been proposed looking for improving individual extractive properties of pure ILs in the
aromatic extraction[2]. However, experimental data related to the purification step demanded by the
extract stream from the extraction unit using ILs are scarce yet.
The aim of this contribution was the determination of vapor-liquid equilibria (VLE) for the
aromatic extract stream withdrawn from the liquid-liquid extraction of toluene from heptane with
1-ethyl-3-methylimidazolium dicyanamide ([emim][DCA]) and 1-ethyl-4-methylpyridinium
bis(trifluoromethylsulfonyl)imide ([4empy][Tf2N]) pure ILs.
Also an {[emim][DCA] +
[4empy][Tf2N]} mixture with a 0.3 mole fraction of [4empy][Tf2N]} was used because it has shown
extractive properties better than those of sulfolane for the extraction of toluene from heptane and
adequate densities and viscosities[2]. Isothermal VLE data at 323.2, 343.2, and 363.2 K, considering
the habitual extraction temperature and the maximum IL operation temperatures[3], have been
determined by headspace gas chromatography. The experimental data shows that the presence of
ILs in the aromatic extract stream improves the relative volatility of heptane in relation to toluene,
allowing for an easy heptane separation by extractive distillation. In addition, the NRTL
thermodynamic model was used to properly adjust VLE data.
References
[1] Meindersma GW, Hansmeier AR, de Haan AB, Ind. Eng. Chem. Res., 2010, 49: 75307540.
[2] Larriba M, Navarro P, Garca J, Rodrguez F, Sep. Purif. Technol., 2013, 120: 392401.
[3] Navarro
P,
Larriba
M,
Garca
J,
Rodrguez
F,
J.
Chem.
Thermodyn.
http://dx.doi.org/10.1016/j.jct.2014.03.023.
M23
2014,
Role of the physicochemical properties of a phosphonium-based ionic liquid on

the interface and performance of lithium battery electrodes
Gaetan Girarda, Matze Hildera, Patrick Howletta, Michael Moserb, Serguei Zavorineb,
Douglas R. MacFarlanec, Maria Forsytha
a
Institute for Frontier Materials, Deakin University, Burwood, Victoria

b
Cytec Canada Inc., Niagara Falls, Canada
c
School of Chemistry, Monash University, Clayton Campus, Australiac
The interaction of a phosphonium-based room temperature ionic liquid (RTIL) with a lithium salt,
lithium bis(fluorosulfonyl)imide, as a function of temperature and concentration has been evaluated
and correlated with the mechanism of lithium transport. The formulated system could be a potential
safe electrolyte for lithium batteries to meet the challenges presented by emerging battery
technologies. The relationship between the physical properties and the mobility of the species
present in solution has also been investigated.
A combination of differential scanning calorimetry (DSC), electrochemical impedance
spectroscopy (EIS), cyclic voltammetry (CV) and nuclear magnetic resonance (NMR) spectroscopy
techniques were used to characterise the system. Impedance spectroscopy measurements established
that the addition of lithium bis(fluorosulfonyl)imide to the ionic liquid decreased the ionic
conductivity over a range of temperatures (from -20 to 120C) and this was related to an increase of
the dynamic viscosity. Interestingly, the mechanism of lithium transport is dependent on the lithium
concentration. It is also evident from EIS and NMR that the mobility of the species in solution is
dependent on lithium salt concentration, and this impacts the electrolyte transport properties and
mechanism. These data give an insight into the fluidity of the species when introducing lithium into
the system.
In terms of lithium electrodeposition, cyclic voltammetry (CV) is a powerful tool to better
understand the electrochemical stability of lithium metal in the electrolyte to demonstrate the
viability of using a lithium based anode in a battery. Cyclic voltammetry measurements showed that
reversible electrodeposition of lithium at a nickel electrode could be observed at a concentration of
0.5 mol.kg-1 of lithium salt at 25C. An increase of lithium concentration also revealed a decrease in
the rate of reoxidation of deposited lithium metal in solution. These data provided an insight into
the fundamental mechanism of lithium transport. The results suggest that the binary systems behave
as a potential electrolyte including improved safety and stability.
M24
Design of ion transport membranes using liquid crystalline structured

polymerizable ionic liquids
Nicolas Goujona*, Nolene Byrnea, Maria Forsytha
a
Institue for Frontier Materials, Deakin University, Geelong, Australia

*Corresponding authors e-mail address: nicolas.goujon@deakin.edu.au
The development of membrane technologies with selective ion channels is an ongoing area of
research. The design of highly selective membranes could be a promising solution for solving many
critical problems including CO2 capture, water/air purification and desalination for drinkable water.
Much effort has been focused on the development of advanced membrane with transport channels
including carbon nanotube membranes and porous polymer membrane
A promising route in the conception of advanced porous membrane with selective transport channel
is the use of ionic liquid crystals (ILCs)1,2, acting as a structure-directing template. ILCs, in
particular the lyotropic subclass, could exhibit a wild range of nanostructure (lamellar, hexagonal,
cubic etc) as function of solvent concentration.3
Here, we have designed a new ionic liquid crystal with a polymerizable moiety
(1-hexadecyl-3-methylimidazolium acrylate). This ILCs have been shown to exhibit the formation
of a liquid crystalline phase upon the addition of water or either water and poly(ethylene glycol)
diacrylate. We have been successfully able to polymerizable this liquid crystalline phase via UV
polymerization resulting to nanostructured polymer film.
Using a combination of polarized optical microscopy, differential scanning calorimetry,
quadrupolar coupling NMR and pfg-NMR, we investigated the phase behavior of ternary systems
involving 1-hexadecyl-3-methylimidazolium acrylate, water and poly(ethylene glycol) diacrylate
prior and after polymerization as well as their transport properties.
References
[1)]
Yoshio, M.; Kagata, T.; Hoshino, K.; Mukai, T.; Ohno, H.; Kato, T. Journal of the American Chemical Society
2006, 128, 5570.
[2]
Mauter, M. S.; Elimelech, M.; Osuji, C. O. ACS nano 2010, 4, 6651.
[3]
Batra, D.; Seifert, S.; Firestone, M. A. Macromolecular Chemistry and Physics 2007, 208, 1416.
M25
Prediction of effective ionic liquids extraction solvents by COSMO-RS

Grabda Mariusza,b, Oleszek Sylwiaa,b, Panigrahi Mrutunjaya, Kozak Dmytroa, Etsuro Shibataa, Nakamura Takashia
a
Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University, Sendai, Japan
b
Institute of Environmental Engineering of the Polish Academy of Sciences, Zabrze, Poland
*mariusz@mail.tagen.tohoku.ac.jp
Solvent extraction is one of the most promising techniques for the recovery of Neodymium and
Dysprosium from spent permanent magnets, however, no practical recycling process has been
commercialized due to the high cost.
Ionic liquids (ILs) have recently been widely promoted as interesting clean alternatives to classical
extraction solvents, because of their unique properties.
Purpose of our study was to select some most effective ionic liquids (ILs) extraction solvents for
NdCl3, using theoretical COSMO-RS model based on quantum chemistry and statistical
thermodynamics of predefined NdCl3-ILs systems. The quantum chemistry package of Turbomole
was used to optimize geometries of all molecules, while solute-solvent interactions were calculated
using the COSMOthermX software.
Predicted, in this way, chemical potentials of NdCl3 in 4,400 different ionic liquids, revealed
significant decreases in values of the chemical potentials in systems with ionic liquids based on one
specific cation of dodecyl-dimethyl-3-sulfopropylammonium, and 3 specific anions of
bis(2,4,4-trimethylpentyl)phosphinate, decanoate, and benzoate.
Considering the additionally predicted physicochemical properties (KOW, viscosity) of the ionic
liquids containing the specific ions, most effective ILs extraction solvents for liquid-liquid
extraction of NdCl3 were selected. Our initial experimental study on a real usefulness of the selected
ILs will be presented at the conference
References
[1] Hoogerstraete, T.V., Onghena, B., Binnemans, K., Int. J. Mol. Sci., 2013, 14(11): 2135321377.
[2] Hoogerstraete, T.V., Onghena, B., Binnemans, K., Int. J. Mol. Sci., 2013, 14(11): 2135321377.
[3] Wellens, S., Thijs, B., Mller, C., Binnemans, K., Phys. Chem. Chem. Phys., 2013, 15: 9663-9669.
[4] Cieszynska, A., Wi!niewski, M., Hydrometallurgy, 2012, 113114: 7985.
[5] Rout, A., Binnemans, K., Dalton Trans.2014, 43: 1862-1872.
M26
Robust and Versatile Ionic Liquids Microarray Achieved by Microcontact

Printing
Christian A. Gunawan, Mengchen Ge, Richard Gondosiswanto and Chuan Zhao*
School of Chemistry, The University of New South Wales, Sydney, Australia
*chuan.zhao@unsw.edu.au
Lab-on-a-chip and miniaturised systems have gained significant popularity motivated by dramatic
differences in material performance at the micron to nano scale realm such as material conservation,
fast response or reaction time, and high product yield.1-3 Nevertheless, to fully exploit micro- to
nano-scale chemistry, solvent volatility and lack of reproducibility problems need to be solved.
In this works, we combine the non-volatile and versatile nature of ionic liquids with microcontact
printing in order to establish a facile protocol for high throughput fabrication of open quasi-2
dimentional microreactors and microfluidics.4 Self-assembled monolayers (SAMs) were patterned
onto gold and glass substrates. Ionic liquids selectively adsorb onto the micropatterned surface and
form stable ionic liquid microdroplets.
The micropatterned ionic liquid droplets have been demonstrated as open micro-electrochemical
cells and photoreactors for microfabrication of metals and charge transfer complexes, substrates for
immobilisation of protein forming biological microarray and as membrane-free high-performance
amperometric gas sensor array.
The results suggest that miniaturised ionic liquid systems can be used to solve the problems of
solvent volatility and slow mass transport in viscous ionic liquids in lab-on-a-chip devices, thus
providing a versatile platform for a diverse number of applications.
References
[1] J. Hogan, Nature, 2006, 442, 351-352.
[2] P. Dubois, G. Marchand, Y. Fouillet, J. Berthier, T. Douki, F. Hassine, S. Gmouh and M. Vaultier, Anal. Chem.,
2006, 78, 4909-4917.
[3] H. J. Ding, S. Sadeghi, G. J. Shah, S. P. Chen, P. Y. Keng, C. J. Kim and R. M. van Dam, Lab on a Chip, 2012, 12,
3331-3340.
[4] C. A. Gunawan, M. Ge and C. Zhao, Nature Comm. 2014, 5: 3744.
M27
Solubility of Carbon Dioxide in Aqueous Solution of

1-Aminopyl-3-Methylimidazolium Bromide with Hydrate Formation
Kaihua Guo!, Yin Bi, Cuilian Yang and Song Li
School of Engineering, Sun Yat-Sen University, Guangzhou, 510275, China
E-mail: guokaih@mail.sysu.edu.cn
Nowadays, the research on efficient processes and environmental friendly materials for CO2
capture in energy engineering has been motivated by the global worming and environmental
aspects. Ordinarily, CO2 capture is dominated by amine-based technologies but those conventional
methods lead to energy intensive and environmental unfriendly due to emissions of the used
volatile solvent components. The new possible ways for effective CO2 capture includes using ionic
liquids (ILs) and their aqueous solutions. The functional ionic liquids (IL) with amino-base have
shown an excellent selective absorption rate for CO2, and its aqueous solution has also shown a
wonderful absorbability of CO2 with the CO2 hydrate formed in the system at temperature
approaching to 0.
In the presented study, the phase equilibrium and solubility property of CO2 in aqueous solution
of 1-Aminopyl-3-Methylimidazolium Bromide [APMIm][Br] with water mass fraction 55%, 65%,
75%, 85% and 95%, at range of 275.15 to 348.15 K and up to 6.5 MPa were studied by means of an
transparent glass vessel in a temperature controlled air bath. The results indicates that the increase
of water could greatly improve the CO2 absorption and hydrate formation rates in [APMIm][Br]
aqueous solution. The CO2 solubility data was obtained and a thermodynamic model was applied
to explain the interaction among [APMIm][Br] solution, gas hydrate and CO2. It provides good
fundamental for the further design of CO2 capturing processes with both gas absorption and
hydrate formation in IL aqueous solutions.
Keywords: carbon dioxide, solubility, ionic liquid, [APMIm][Br], aqueous solution,
Corresponding author (Presenter): Phone: +86-20-39332893 Fax +86-20-39332895 E-mail: guokaih@mail.sysu.edu.cn
M28
Solubility of CO2 in Ionic Liquids Analogous: Experiments and Modeling

Mohamed K. Hadj-Kali, Sarwono Mulyono, Emad Ali, Inas Alnashef
King Saud University, Chemical Engineering Department, Riyadh, Saudi Arabia
* mhadjkali@ksu.edu.sa
Low cost ionic liquid analogues, namely, deep eutectic solvents (DESs), have attracted more
attention for use in a diversity of applications. DESs exhibit many favourable properties, such as
availability, non-toxicity, biodegradability, recyclability, non-flammability and low price.
In this work, phosphonium-, ammonium- and choline chloride-based DESs with different hydrogen
bond donors (HBD) have been synthesised. Then, the solubility of carbon dioxide in these DESs at
a fixed pressure and temperature was determined experimentally.
It was concluded that the use of mono-ethanol amine (MEA) as the HBD improved the solubility
substantially. Moreover, samples of the DES before and after the absorption of the CO2 were
analysed using HPLC (Figure 1). The results showed that only 10% of the amine reacted with the
CO2 (Figure 1.a) while for the aqueous solution of MEA, all of the amine reacted with the CO2
(Figure 1.b). Moreover, using DSC (Differential Scanning Calorimeter) we also found that specific
heat of the amine based DES is about half that for water, 1.91 against 3.21 kJ!mole-1!K-1,
respectively. These results imply that the energy needed in the regeneration step in the case of DES
is lower than that for the amines aqueous solutions.
Furthermore, a mathematical model based on the Peng-Robinson (PR) equation of state (EoS) was
developed to correlate the CO2 solubility in these types of DESs. The model was validated with the
obtained experimental data and tested with other specific DESs reported in the literature over a
wide range of temperature and pressure values. In general, there was a good agreement between the
experimental and calculated data. The obtained model can be utilised to study the effectiveness of
using DES in CO2 capturing processes or any other separation processes.
'
0+123+,45#,678239:)2.
;1:+3,45#,678239:)2.
!"&
'
!"&
!"%
!"%
!"$
!"$
!"#
!"#
0+123+,45#,678239:)2.
;1:+3,45#,678239:)2.
!
!
&
'!
()*+,-*)./
&
'!
()*+,-*)./
(1.a) Choline Chloride MEA DES
(1.b) MEA 30 wt%
Figure 1. HPLC analysis of the fresh solvent before CO2 absorption (continuous line) and after the CO2 absorption
(dashed lines) in (a) Choline Chloride MEA DES and (b) Monoethanolamine (MEA) aqueous solution (30 wt%).
M29
Hydrogen Evolution at Semiconductor - Ionic Liquid Interfaces

Ahmed Halimaa*, Vijayaraghavan Ranganathana, Douglas R MacFarlanea,
a
School of Chemistry, Monash University, Clayton, Australia

* ahmed.halima@monash.edu
A hydrogen-based energy technology is one of the most promising alternatives to fossil fuel use.
Solar-driven photo-electrochemical generation of hydrogen gas from solvated protons in
electrolytes is highly dependent on the catalytic efficiency of the electrolyte interface with the
electrode material[1]. Even in the dark, almost all semiconductors suffer serious deterioration upon
interfacing with aqueous media. The use of low, or zero, water content protic Ionic Liquid
electrolytes offers the potential of increased stability and highly favorable proton transfer
mechanisms. The present work considers hydrogen generation from a variety of Ionic Liquids/acid
mixtures, and investigates the stability and performance of semiconductor electrodes in dark and
under illumination. Semiconductors considered include silicon and also silicon coated with Boron
doped diamond that has been shown to both protect silicon and support efficient proton reduction
kinetics[2].
References
[1] M.G. Walter, E.L. Warren, J.R. McKone, S.W. Boettcher, Q. Mi, E.A. Santori, N.S. Lewis,
Chem Rev, 110 (2010) 6446-6473.
[2] A.F. Halima, U.A. Rana, D.R. MacFarlane, Electrochimica Acta, 115 (2014) 639-643.
M30
What effect does varying the anion and the cation of an ionic liquid have on the
dissolution of the different components of biomass?
William Hart,* Jason Harper, Leigh Aldous
University of New South Wales, Sydney, Australia
*w.hart@unsw.edu.au
Biomass is primarily made up of cellulose and lignin.[1] Cellulose is a linear polymer of glucose
which can be enzymatically broken down into simple sugars if it can be ioslated from the bulk of
the biomass. Lignin is a complex aromatic bioploymer, made from the polymerisation of phenolic
compounds found in nature.[2] For either of these compounds to be used industrially, they must first
be separated, both from each other and from the rest of the materials found in biomass.
Previous reports have described the use of ionic liquids for the dissolution of various types of
biomass.[1] This project looked at the effects of varying the anion and the cations of ionic liquids on
their ability to dissolve cellulose and lignin.
During the course of this project it was seen that there is a dramatic change in lignin solubility on
changing the cation of the ionic liquid,[Figure 1] as has been seen previously for cellulose.[1] It was
also seen that ionic liquids with more strongly coordinating anions [Figure 2] are better solvents for
the dissolution of cellulose, while changing the anion of an ionic liquid has little effect upon the
dissolution of lignin at room temperature.
Figure 1: The ionic liquid cations studied.
Figure 2: Some of the ionic liquid anions studied.
References
[1]
[2]
Brandt A, Grasvik J, Hallett J, Welton T, Green Chem., 2013, 15: 550-583.

Zakzeski J, Bruijnincx P, Jongerius A, Weckhuysen B, Chem. Rev., 2010, 110: 3552-3599.
M31
Novel chloroimidazolium-based ionic liquids: preparation, characterisation and

behaviour as solvents to control reaction outcome
Rebecca R. Hawker,* Leigh Aldous, Jason B. Harper
University of New South Wales, Sydney, Australia
*rebecca.hawker@unsw.edu.au
Through changing the components of ionic liquids, their physical properties can be altered, such
that they might be considered designer solvents.[1] This design might be extended with
task-specific ionic liquids being conceived, prepared and investigated to control reaction outcome,
above what is currently available.[2]
The focus of this project is a series of novel chloroimidazolium-based ionic liquids (Figure 1).
These were chosen because it was of interest to examine the effect of adding electron withdrawing
groups to the cation, on both the physical properties of the resulting ionic liquid and how the
solvent affects reaction outcome.
Cl
N
N
Cl
1
Cl
Cl
N
N
[Tf 2N] -
[Tf 2N] -
[Tf 2N] 2
Figure 1. The novel chloroimidazolium-based ionic liquids studied in this project.

Along with their synthesis, properties of the ionic liquids (including density, viscosity and
electrochemical window) will be discussed. Only small changes were observed relative to the
parent ionic liquid, demonstrating that (in practical terms) these ionic liquids were interchangeable.
In terms of reaction outcome, however, significant changes were observed in the solvent effects on
well-studied reactions (including the Menschutkin reaction [2-4] shown in Scheme 1). Importantly,
the outcomes could be readily described in terms of the interactions of reagents with the modified
cation, demonstrating that these modifications can be used to predictably affect reaction outcome.
Scheme 1. The Menschutkin reaction between benzyl bromide 1 and pyridine 2 giving the
corresponding pyridinium bromide product 3.
References
[1] Harper J, Kobrak M, Mini-Rev. Org. Chem., 2006, 3: 253-269.
[2] Tanner E, Yau H, Hawker R, Croft A, Harper J, Org. Biomol. Chem., 2013, 11: 6170-6175.
[3] Yau H, Croft A, Harper J, Faraday Discuss., 2012, 154: 365-371.
[4] Yau H, Howe A, Hook J, Croft A, Harper J, Org. Biomol. Chem., 2009, 7: 3572-3575.
M32
Low viscosity phosphonium-based ionic liquid for electrolytes

Matthias Hildera, Gaetan Girarda, Serguei Zavorineb, Patrick Howletta, Michael Moserb, Douglas MacFarlanec, Maria
Forsytha
a
Institute for Frontier Materials, Deakin University, Burwood, Australia

b
Cytec Canada Inc., Niagara Falls, Canada
c
School of Chemistry, Monash University, Clayton Campus, Australia
*m.hilder@deakin.edu.au
Ionic Liquids (ILs) have many beneficial properties making them attractive electrolyte alternatives
for high voltage energy applications. They fulfil the basic electrolyte requirements being: (i) they do
have low melting points; (ii) show ionic conductivity; (iii) display electrochemical stability.
Additionally their have a negligible vapour pressure are generally non-flammable, which are other
beneficial properties for practical applications.
Here the physiochemical properties of various phosphonium based ionic liquids with
bis(fluorosulfonyl)imide (FSI) or bis(trifluoromethane)sulfonimide (TFSI) anions are investigated
including thermal phase change behaviour, viscosity, ionic conductivity and electrochemical
stability. In addition the effect of lithium addition is studied for 0.5 and 1.0mol/Kg samples
including lithium cycleability using cyclic voltammetry techniques.
It is shown that in general the FSI ILs perform better than the TFSI analogues in terms of viscosity
and conductivity while the electrochemical window is better for the TFSI samples. The addition of
lithium salts increases viscosity and lowers conductivity. An interesting observation is that small
alkyl TFSI phosphonium ILs are solids at room temperature but once they melt they show a very
low viscosity and high conductivity. They also show reversible lithium cycling making them
promising candidates for electrolyte applications in devices such as lithium batteries.
M33
Removal of nitrogen compounds for improved efficiency of desulphurization of

diesel using ammonium-based Deep Eutectic Solvents
Hanee F. Hizaddina*, Anantharaj Ramalingama, Moh. Ali Hashima, Mohamed K.O. Hadj-Kalib
a
University of Malaya Center for Ionic Liquids (UMCiL), Department of Chemical Engineering, Faculty of Engineering,
University of Malaya, 50603 Kuala Lumpur, Malaysia
b
Chemical Engineering Department, King Saud University, P.O.Box 800, Riyadh, 11421, Saudi Arabia
*hanee.hizaddin@gmail.com
In the pursuit of producing clean fuels, the oil refinery industry is under increasing pressure
to produce low-sulphur liquid fuels with the ultimate target of zero emission. The presence of
aromatic nitrogen compounds in the diesel processing feed inhibits the efficiency of the
hydrodesulphurization (HDS) process through competitive adsorption and catalyst deactivation.
Thus, in order to improve the efficiency of HDS process, it is necessary to remove refractory
aromatic nitrogen compounds from the HDS feed. Conventional process for removal of nitrogen
compound is hydrodenitrogenation (HDN) process, which is energy intensive and operates under
severe conditions. Liquid-liquid extraction process is an attractive alternative to HDN due to its
mild operating condition while maintaining the chemical constituents of the species involved.
However, the efficiency of this process depends highly on the choice of solvent. A novel class of
solvent, namely Deep Eutectic Solvents (DESs) has the potential to be used as an extractive solvent
due to its favorable chemical properties, especially its negligible vapor pressure and thus no
emission of volatile toxic chemicals and reduced loss of solvent. DES is a combination of two or
more chemical constituents which produce a eutectic mixture in liquid form at room temperature.
Recently, DESs have been used for the separation of aromatic/aliphatic mixture[1], separation of
azeotropic mixture[2] and desulphurization of diesel[3] at research scale. In this work, quantum
chemical methods were used to screen potential DESs for the removal of 5-membered (non-basic)
and 6-membered (basic) nitrogen compounds from diesel. It was observed that ammonium-based
DESs provide high selectivity towards aromatic nitrogen compounds. Thereafter, ternary
liquid-liquid equilibria experiment was performed to investigate and validate the performance of
four ammonium-based DESs in extracting basic and non-basic nitrogen compounds from model
diesel. The experimental tie lines were then compared against calculated tie-lines determined by the
fully-predictive Conductor-like Screening Model for Real Solvents (COSMO-RS) with root mean
square deviation (RMSD) of less than 10%.
References
[1] M.A. Kareem, F.S. Mjalli, M.A. Hashim, M.K.O. Hadj-Kali, F.S. Ghareh Bagh, I.M. Alnashef, J. Chem.
Thermodyn., 2013, 65:138-149.
[2] F.S. Oliveira, A.B. Pereiro, L.P.N. Rebelo, I.M. Marrucho, Green Chem., 2013, 15:1326-1330.
[3] C. Li, D. Li, S. Zou, Z. Li, J. Yin, A. Wang, Y. Cui, Z. Yao, Q. Zhao, Green Chem., 2013, 15:2793-2799.
M34
Proton and HSCQ NMR of Cellulose and Wood in ionic liquids

Ashley Holding, Valterri Mkela, Ilkka Kilpelinen, Alistair W. T. King,*
a
University of Helsinki, Department of Chemistry, Laboratory of Organic Chemistry, Helsinki, Finland

*alistair.king@helsinki.fi
Previously, solution-state cellulose has been probed by 1H NMR with the use of totally deuterated
solvents or by the use of complicated solvent-suppression techniques; and, in addition, conflicting
resonances from the solvent often in the cellulose backbone peak region. Here we present a simple
procedure without these drawbacks, based on dissolution in [PRRRR][OAc] ionic liquids and
d6-DMSO allowing for conflicting-resonance free 1H NMR spectra, leading to the full assignment
of cellulose from HSCQ. These ionic liquids have been previously shown to dissolve lignin and
cellulose with the addition of polar-aprotic co-solvents [ref]. Interestingly, reducing end-groups
(C1, C4 alpha and beta) from the cellulose are clearly visible in the 1H spectrum [Figure 1],
allowing useful information about the state of cellulose in the solution state to be gained.
Integration values of the reducing end-group signals were correlated with molecular weights and
DP values obtained from GPC of the cellulose polymers (Gel Permeation Chromatography).
Thereafter it is shown that integration value ratios of C1, and C4 alpha and beta peaks from the 1H
NMR spectrum can be used to predict the DP of the cellulose in solution. Dissolution of celluloses
from a wide molecular weight range in phosphonium ionic liquid-DMSO solutions is possible, from
Cellobiose to Microcrystaline Cellulose (MCC) to Pre-Hydrolysis Kraft Pulp (PHK). All cellulose
samples were dissolved in a solution of the ionic liquid [P8881][OAc] and DMSO, in a 60%-40%
ratio, by stirring for 100oC for 1 hour. Cellulose samples studied include Cellobiose,
Microcrystaline cellulose (MCC), scCO2 extracted Cellulose (DP15), Cellulose (DP60), Avicel,
Borregard pre-hydrolysis kraft pulp (PHK) and Bahia PHK. Other biopolymers studied included
dioxane acidolysis spruce lignin, norway spruce galactoglucomanan (a hemi-cellulose model), in
addition to whole biomass: auto-hydrolysed spruce wood (1 mm, wiley milled). This simple NMR
technique opens the door to in-situ monitoring of hydrolysis or homogenous derivatization reactions
in addition to structural analysis of whole wood components after dissolution.
Figure 1a) HSCQ of MCC 8wt% in [P8881][OAc]/DMSO 1b) C1 signal and terminal signals of
cellulose samples
References
[1] Holding, A. J.; Heikkil, M.; Kilpelinen, I.; King, A. W. T. ChemSusChem 2014, 7, 142234.
M35
Ionic Liquids Containing Cationic Metal-Chelate Complexes [ML1L2](Tf2N)

(M = CuII, NiII, PdII; L1 = diamine ligands; L2 = diketonate ligands)
Hitoshi Hosokawa, Yusuke Funasako, Tomoyuki Mochida*
Recently, many ionic liquids with interesting physical properties have been reported. Herein, we
report on the preparation and properties of a series of metal-containing ionic liquids with cationic
chelate complexes (Fig. 1a).[1,2] These liquids exhibit reversible changes in color, thermal properties,
and magnetic properties in response to organic solvent vapors.
The CuII-containing complexes are purple liquids at room temperature and change color to
blue-purple, blue, or green when exposed to different organic vapors. This color change is caused
by coordination of the vapor molecules to the cation, and the resultant colors depend on the
coordination strength (donor number, DN) of the vapor molecules. The complex bearing a long
alkyl chain changes from a purple solid to a brown liquid at its melting point. The NiII-containing
complex is a dark red diamagnetic liquid and changes to a green paramagnetic liquid when it
absorbs vapors with a high DN (Fig. 1b). The PdII-containing complexes are yellow solids, melt at
temperatures below 100 C, only assume square-planar coordination geometry, and do not respond
to organic solvent molecules. X-ray crystal structure determination revealed the tendency of the
cations to form dimer-like arrangements, which increases the melting points and viscosities of the
complexes.
We prepared Nafion films incorporating the NiII-containing cations. These films exhibit color
change in response to organic solvents and their vapors,[3] further, the films show thermochromism
when appropriate solvent molecules are incorporated (Fig. 1b). Thus, these materials are useful for
solvent recognition, vapor detection, and temperature sensors.
Fig. 1. (a) Structural formulae of the vapor-responsive ionic liquids. (b) Photographs of ionic liquids
(M = Ni) before and after the absorption of organic solvent vapors (top), and Nafion films
incorporating appropriate solvent molecules at various temperatures (bottom).
References
[1] Funasako Y, Mochida T, Takahashi K, Sakurai T, Ohta H, Chem. Eur. J., 2012, 18: 11929-11936.
[2] Hosokawa H, Funasako Y, Mochida T, Dalton Trans., 2014, 43: 6864-6869.
[3] Funasako Y, Mochida T, Chem. Commun., 2013, 49: 4688-4690.
M36
Catalysed Lignin Depolymerisation using Polyoxometalate Electrochemical

Mediators in Ionic Liquids
Md. Mokarrom Hossain, Leigh Aldous*
*e-mail addres: l.aldous@unsw.edu.au
Fossil fuel sources provide us with the majority of aliphatic and aromatic chemicals which we use
to make plastics, pharmaceuticals, colorants, etc. As demand continues to increase and fossil fuel
continues to be depleted, lignocellulosic biomass is being considered as a sustainable alternative
source of aromatic compounds. Ionic liquids are non-volatile, relatively safe solvents which can be
designed to completely dissolve lignocellulosic biomass.1 These dissolved components (cellulose
and lignin) are highly amenable to subsequent chemical transformation and treatment, and can be
easily separated from the ionic liquid by the simple addition of an anti-solvent such as water or
ethanol.2
In this study we have investigated Polyoxometalates (or POMs) as simple mediator species for the
depolymerisation of lignin dissolved in ionic liquids. By altering the POMs structure we can alter
their reactivity and thus depolymerisation products, ideally allowing the isolation of defined
aromatic fractions.
We have investigated a range of polyoxometalates in the presence of lignin model compounds,
genuine wood lignin and whole wood (dissolved into ionic liquids). The polyoxometalates were
cycled through their various redox states using electrochemistry. The continual regeneration of the
active polyoxometalate state allows them to be used as catalytic mediators for the depolymerisation
of the solubilised lignin.
Figure 1: Scheme of lignin depolymerisation using POMs (left) and cyclic voltammogram for various
amount of wood in presence of 20 mM phosphotungstate in [Emim][OAc] (right).
References:
1. M. M. Hossain, L. Aldous, Aust. J. Chem. 2012, 65, 1465.
2.
N. Sun, M. Rahman, Y. Qin, M. L. Maxim, H. Rodriguez, R. D. Rogers, Green Chem. 2009, 11, 646.
M37
Imidazolium-based Distillable Ionic Liquids for Lignocellulosic Biomass

Processing
Md. Mokarrom Hossain, Leigh Aldous*
*e-mail addres: l.aldous@unsw.edu.au
The demand for energy and materials is always increasing, and our fossil fuels continue to be
depleted. There is an urgent need for sustainable alternatives. Lignocellulosic biomass is composed
of (primarily) cellulose, which can be considered as a renewable alternative for at least some of our
energy demand. If suitably designed, ionic liquids (ILs), are able to dissolve biomass components
partially or completely.1,2 Ideally such ILs should have anions with high hydrogen bonding basicity
and cations capable of !-!-interactions.1 The dissolved cellulose can also be separated by the
subsequent addition of anti-solvents (e.g. water, acetone) at which stage enzymatic hydrolysis and
other chemical processing is much more efficient.2
In this study,3 we have demonstrated the dissolution of wood in different ILs, followed by isolation
and enzymatic conversion of the cellulosic fraction to glucose, a precursor to bioethanol. Novel
protic ILs were compared and contrasted with their widely used aprotic analogue, with our new
protic ILs being significantly cheaper and easier to prepare. Treatment of wood with one of our new
ILs, [Eim]Cl, resulted in excellent conversion to glucose upon enzymatic hydrolysis. In addition,
[Eim]Cl could be efficiently recycled by taking advantage of its protic nature, such that it was ca.
98% recoverable for further use with no structural change.
!
Figure 1: Distillation of [Eim]Cl (left) and enzymatic conversion of various ILs-treated wood (right).
References:
2. N. Sun, M. Rahman, Y. Qin, M. L. Maxim, H. Rodriguez, R. D. Rogers, Green Chem. 2009, 11, 646.
3. M. M. Hossain, L. Aldous, Submitted, 2014
M38
High Yield Access to Imidazolium-based Fluorous Ionic Liquids

Michael Hummela, Michael Noisternigb, Ulrich J. Griesserb, Klaus Wursta, Gerhard Lausa, Herwig Schottenbergera,*
a
Institute of General, Inorganic and Theoretical Chemistry, Leopold-Franzens University Innsbruck, Innrain 80,
Institute of Pharmacy, Department of Pharmaceutical Technology, Leopold-Franzens University Innsbruck, Innrain 52,
A-6020 Innsbruck, Austria, not Australia
*herwig.schottenberger@uibk.ac.at
The possibility of tailoring the properties of ionic liquids (ILs) has been demonstrated countless
times.
In particular, the solvent properties of ILs can be adjusted and fine-tuned to render a wide variety of
monomeric and polymeric inorganic and organic substances soluble.
Even amphiphobic organofluorine compounds with a low affinity to common molecular solvents
can be dissolved in task-specific ILs bearing highly fluorinated side chains.
Fluorocarbon-based compounds have both technical and medical applications such as
fluorosurfactants or refrigerants, as anesthetics and ocular tamponades, or even as doping agents.
However, many organofluorocarbon derivatives have raised eco-toxicological and environmental
concerns, and thus require special technical measures of process containment and recycling
methodologies.
Fluorinated ionic liquids (FILs) have been found to be excellent solvent media capable of
fluorocarbon capture and sequestration [1]. However, the use of FILs is often limited due to costly
and low yielding syntheses.
Herein we present a set of FILs easily accessible by perfluoroalkyl-2-ethylations of starting
2-mercaptoimidazoles.
References
[1] Pereiro AB, Arajo JMM, Martinho S, Alves F, Nunes S, Matias A, Duarte CMM, Rebelo LPN, Marrucho IM, ACS
Sustainable Chem. Eng. 2013, 1:427439.
M39
Amino Acid Ionic Liquids as Self-organization Media of Amphiphilic Molecules

Takahiro Ichikawa1,2, Kanae Fujimura1,2, Masafumi Yoshio3, Takashi. Kato3, and Hiroyuki Ohno1,2*
a
Tokyo University of Agriculture and Technology, Tokyo, JAPAN

b
Functional Ionic Liquid Laboratoris, JAPAN
c
The University of TokyoTokyo, JAPAN
*e-mail : ohnoh@cc.tuat.ac.jp
Abstract: We have previously succeeded in preparing amino acid ionic liquids (AAILs) using
natural amino acids as anions[1]. These AAILs have various unique characteristics and therefore
attracted significant attentions. In particular, their superior hydrogen-bonding ability stimulates us
to envision that these AAILs have a great potential to be new solvent alternative to water. In liquid
crystal science, water is an essential solvent that helps self-organization behavior of amphiphiles.
Liquid-crystalline materials composed of amphiphiles and solvents are categorized into lyotropic
liquid crystals. They form various nanosegregated structures depending on their concentrations and
solvents. Focusing on a unique characteristic of AAILs that their physicochemical properties are
tunable via selection of amino acid anions, we have expected that the use of AAILs provides a
novel lyotropic liquid-crystalline system whose self-organization behavior can be controlled
through the design of AAILs.
In the present study, we have synthesized six AAILs
consisting of 1-butyl-3-methylimidazolium ([bmim])
cation and amino acid anions, such as glycine, L-alanine
([Ala]), L-leucine, and L-serine. As an amphiphilic
molecule,
N-{3-[N,N-bis(2-hydroxyethl)aminopropyl]}
-3,4-didodecyloxy benzoylamide
was prepared as
[2]
previously reported . These AAILs were mixed with the
Figure 1. Structure of amphiphilic
amphiphile in various molar ratio, and their
molecule and amino acid ionic liquids
used in this study.
co-organization behavior was examined. These mixures
showed a variety
of liquid-crystalline phases including bicontinuous cubic (Cubbi) LC phases through
nanosegregation between the ionophilic and ionophobic parts[3]. For example, the mixture of the
amphiphile and [bmim][Ala] in a 9:1 molar ratio formed hexagonal columnar (Colh) and Cubbi
phases. On the other hand, mixture in a 7:3 molar ratio exhibited only a smectic phase excluding
the formation of Colh and Cubbi phases. These changes in the mesophase patterns were considered
to be induced by the cooperative organization between the amphiphilic molecule and AAILs. These
results provide the potential usability of AAILs as self-organizing medium of amphiphilic
molecules. Relationships between hydrogen-bonding donor/acceptor abilities of AAILs and
self-organization behavior of the amphiphilic molecule in AAILs will also be mentioned.
References
[1] Fukumoto K, Yoshizawa M, Ohno H, J. Am. Chem. Soc., 2005, 127: 2398-2399.
[2] Ichikawa T, Yoshio M, Taguchi S, Kagimoto J, Ohno H, Kato T, Chem. Sci., 2012, 3: 2001-2008.
[3] Ichikawa T, Fujimura K, Yoshio M, Kato T, Ohno H, Chem. Commun., 2013, 49: 11746-11748.
M40
Electrolyte Systems and Interfacial Processes in Energy Storage and Conversion

Boyan Iliev, Thomas J. S. Schubert, Jan Wimberg,*
Iolitec Ionic Liquids Technologies GmbH, Heilbronn, Germany
*info@iolitec.de
Supercapacitors (also called electric double-layer capacitors (EDLCs)) and lithium ion batteries
(LIBs) are promising and widely used materials for the important task of energy storage. Therefore,
both technologies are subject of intensive research. Advantageous characteristics such as energy
and power density enable the utilization for various applications. As the utilization of e.g. electronic
cars becomes more and more important in times of fuel shortage, the combined use of LIBs and
EDLCs with different and at the same time complementary properties is of great interest. A way to
increase the performance of such electrochemical devices is to increase the electrochemical stability
of the used electrolyte.
However, serious problems occurred recently through short-circuit currents leading to overheating
and ignition of organic solvent based electrolytes. Therefore, new types of electrolytes are currently
under investigation and caused a great interest in the utilization of ionic liquids (ILs).
Ionic liquids are molten salts that are liquid at temperatures below 100C and consist of variably
substituted ions. ILs are often denoted as designer solvents, since the molecular properties can be
easily tuned by rational design or through new combinations of anions/cations. Their tunable
properties like viscosities, conductivities, chemical and thermal stabilities, large electrochemical
windows and incombustibility up to high temperatures are beneficial for the use as novel
electrolytes[1]. Introduction of specific functional groups to further modify a structure for a specific
application, such as electrolyte for supercaps, lead to the so-called task specific ionic liquids
(TSILs).
We will report on our latest developments in the field of novel ionic liquid based electrolytes for
LIBs and EDLCs. The focus will be given on the use of ILs and suitable additives in order to
enhance the safety of electrochemical devices. Furthermore, we will demonstrate the correlation
between selectively synthesized lead structures and an increased performance of the respective
electrolytes.
References
[1] Wasserscheid, P.; Welton, T. Ionic Liquids in Synthesis, Wiley-VCH, Weinheim, 2003.
M41
Cellulose Dissolution and Regeneration Studies with Triaminocyclopropenium

Ionic Liquids
Owen J. Curnow* and Chaminda Jayasinghe
* E-mail: owen.curnow@canterbury.ac.nz
Triaminocyclopropenium
chloride
salts,
including
the
n-hexane-miscible
hexadecyltriaminocylopropenium chloride salt, have been investigated for their potential as
cellulose dissolution solvents. These salts have been found to have excellent thermal, air and water
stabilities as well as moderately low viscosities[1], and the especially weak cation-chloride
interactions are expected to increase the chloride-cellulose interactions that are essential for
cellulose dissolution. The use of co-solvents was also investigated for their potential to facilitate the
dissolution process.
Cellulose regeneration was carried out using water, ethanol or n-hexane and the properties of the
regenerated cellulose were looked at by Degree of Polymerisation (DP) studies, powder X-ray
diffraction (XRD), and Thermal Gravimetric Analysis (TGA).
References
M42
Absolute pKa Scales of Substituted Benzenethiols in Room Temperature Ionic

Liquids: An Unusual Solvation Effect of Cation
Zhen Wanga,b, Pengju Ji,b * Xin Lia and Jin-Pei Chenga,b *
a
b
*jipengju@mail.tsinghua.edu.cn , jinpei_cheng@mail.tsinghua.edu.cn
15
p-MeO
p-Me
pKa in BmimOTf
p-t-Bu
Slope = -2.53
Intercept = 14.4
2
R = 0.996
14
13
12
11
p-F
p-Cl
p-CF3
p-Br
Slope = -2.48
Intercept = 14.0
2
R = 0.999
-0.4 -0.2 0.0
0.2
0.4
p-NO2
0.6
!p
0.8
1.0
1.2
1.4
Equilibrium acidity (pKa) of fourteen substituted benzenethiols in four pure room temperature ionic
liquids (RTILs), BmimOTf, BmimNTf2, BmpyNTf2, and Bm2imNTf2, were carefully measured and
the corresponding acidity scales were established under standard conditions using the indicator
overlapping method developed previously.[1] Hammett plots show two distinct lines with similar
slopes and excellent linearity (R2 of 0.996-0.999) for various substituents in all four ILs, which may
be rationalized by an enhanced effect of the IL cation to solvate the para substituent of feasible
electronic structure. On the other hand, regression analyses among the pKa scales in the four RTILs
also show a linear relationship with R2 values greater than 0.996.
References:
[1] Wang Z, Deng H, Li X, Ji P, Cheng J-P, J. Org. Chem. 2013, 78, 12487; Deng H, Li X, Chu Y, He J Q, Cheng J-P, J.
Org. Chem. 2012, 77, 7291.
M43
Extraction of lithium using ionic liquid dissolved in tributyl phosphate

Chenglong Shia,b, Yongzhong Jiaa, Yan Jinga*
a
Key Laboratory of Salt Lake Resources and Chemistry, Qinghai Institute of Salt Lakes, Chinese Academy of Sciences,
810008, Xining, China
b
University of Chinese Academy of Sciences, 100049, Beijing, China
*
schenglongqh@163.com
Abstract
In the present work, experiments had been carried out for the solvent extraction of lithium from salt
lake brine with imidazolium based ionic liquid. In this system, the ionic liquid and tributyl
phosphate (TBP) were used as extraction medium and extractant respectively. The effects of
temperature, solution pH value, phase ratio and other factors on the extraction were studied in
detail. The Preliminary experimental results had demonstrated that this ionic liquid system shown
considerable extraction ability for lithium from salt lake brine of a high Mg/Li ratio. This work
promised to provide new efficient media based on ionic liquid for separation lithium from salt lake
brine.
M44
Ionic liquid promoted chemical fixation of CO2 to quinazoline-2,4(1H,

3H)-diones
Wenjing Lu, Jun Ma, Tao Jiang, Jiayin Hu, Jinliang Song, Zhaofu Zhang, Buxing Han*
Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
* Hanbx@iccas.ac.cn
Utilization of CO2 as renewable carbon resource to produce value-added chemicals has received
much attention in recent years. However, development of highly-efficient routes to transform CO2
into value-added chemicals is a long-standing task because of both thermodynamic and kinetic
problems.1,2 In this work, we studied the synthesis of quinazoline-2,4(1H,3H)-diones from CO2 and
2-aminobenzonitriles in different ionic liquids (ILs). It was demonstrated that IL
1-butyl-3-methylimidazolium acetate, which was a simple and easily prepared IL, could act as both
solvent and catalyst, and the reactions could proceed very efficiently at atmospheric pressure of
CO2, and high yield of the products could be obtained at optimized condition. Further study
indicated that the IL was also very efficient for converting other 2-aminobenzonitriles into the
corresponding quinazoline-2,4(1H,3H)-diones in high yields at atmospheric pressure. As example,
the dependence of the quinazoline-2,4(1H,3H)-dione yield on reaction time at 90oC is shown in
Figure 1.
Figure 1. The effect of reaction time on the yield of quinazoline-2,4(1H,3H)-dione at 90oC and
ambient pressure
References
[1] Sakakura T, Choi J C, Yasuda H, Chem. Rev., 2007, 107: 2365.
[2] He M Y, Sun Y H, Han B X, Angew. Chem. Int. Ed., 2013, 52: 9620.
M45
Effect of Amines on the Ionothermal Synthesis of AlPO4-5

Xinge Jianga, Xiaoling Changa, li Zhanga, Jianfeng Wanga, Jun Xua, Li Hana,*
a
School of Chemical Engineering and Energy, Zhengzhou University, Zhengzhou, China

*E-mail address: lihan@zzu.edu.cn
The study of microporous aluminophosphates (AlPO4-n) materials has been highlighted in recent
years as an attractive alternative in designing new materials for adsorption, catalysis, membrane,
sensor, etc[1]. In general, these materials are synthesized by hydrothermal method under high vapor
pressure. There has been great interest in ionothermal synthesis, which is a novel method for
synthesizing molecular sieves using an ionic liquid as both solvent and template[2-4]. Ionothermal
synthesis of molecular sieves can be carried out at ambient pressure because of the very low vapor
pressure of ionic liquids. Compared with the traditional hydrothermal method, this alleviates safety
concerns associated with high pressures.
In the ionothermal synthesis of molecular sieves, the introduced amine affects the dynamics of
the crystallization process and improves the selectivity of the crystallization reaction because of its
structure-directing effect together with the ionic liquid[5]. In this paper, we report the influence of
amines on the ionothermal synthesis of AlPO4-5 molecular sieves in 1-ethyl-2,3-dimethyl
imidazolium bromide ionic liquid ([Edmim]Br).
The synthesis experiment was carried out in an open system. [Edmim]Br (4.96 g) and phosphoric
acid (1.33 g H3PO4, 85%) were mixed, aluminum isopropoxide (1.30 g, Al[OCH(CH3)2]3, 98%,
Aldrich) was subsequently added under vigorous stirring, and then different amine (triethylamine,
di-n-propylamine) was introduced. The final molar composition of the reaction system was Al2O3 :
1.8P2O5 : 75[Edmim]Br : 3.5H2O : 1.5Amine. The system was then heated in an oven at 150 oC for
different time (12 h, 24 h, 48 h, 90 h) and ceased by quench to room temperature after
crystallization. The product was washed thoroughly with distilled water and acetone, respectively,
and then dried at 100 C for other characterization.
The results indicated that AlPO4-5 molecular sieves were successfully synthesized ionothermally
in [Edmim]Br with the presence of amine which plays a cooperative structure directing role along
with [Edmim]Br. In the absence of amine, tridymite denser phase was obtained and AlPO4-5
molecular sieve could not be synthesized. Pure AlPO4-5 molecular sieves were obtained whether
triethylamine or di-n-propylamine was added.
Acknowledgement
This work was supported by the NSFC-Henan Talent Development Joint Fund (Grant No.
U1204215) and the National Natural Science Foundation of China (Grant No. 21206150).
References
[1] Khoo D Y, Kok W M, Mukti R R, Mintova S, Ng E P, Solid State Sciences, 2013, 25: 63-69.
[2] Cooper E R, Andrews C D, Wheatley P S, Webb P B, Wormald P, Morris R E, Nature, 2004, 430: 1012-1016.
[3] Han L J, Wang Y B, Li C X, Zhang S J, Lu X M, Cao M J, AIChE Journal, 2008, 54: 280-288.
[4] Li K D, Tian Z J, Li X L, Xu R S, Xu Y P, Wang L, Ma H J, Wang B C, Lin L W, Angew. Chem. Int. Ed., 2012, 51:
4397-4400.
[5] Wang L, Xu Y P, Wei Y, Duan J C, Chen A B, Wang B C, Ma H J, Tian Z J, Lin L W, J. Am. Chem. Soc., 2006,
128: 7432-7433.
M46
Understanding and predicting organic reaction outcomes in ionic liquids

Sinead Keaveneya, Karin Schaffarczyk McHalea, Ronald R. Hainesa and Jason B. Harpera
a
School of Chemistry, University of New South Wales, Sydney, NSW, Australia, 2052
*E-mail: s.keaveney@unsw.edu.au
Due to their negligible vapour pressure and the possibility of solvent recycling, ionic liquids
are being considered as potential replacements for commonly used and highly volatile organic
solvents[1]. In order for such replacement to be successful, their effect on reaction outcomes must be
readily predicted. Whilst there has been an increase in the understanding of how such solvents
affect reaction outcome[2], controlling reaction outcome using ionic liquids in a predictable fashion
remains elusive. The work in this project seeks to extend the developing predictive framework of
ionic liquid solvent effects and exploit this knowledge to control reaction outcomes.
The focus of the project is on the addition reaction between species 1 and 2 (Scheme 1).
Involving the nucleophilic attack of a nitrogen centre on a carbonyl, this process may be compared
to a substitution reaction studied previously[3], where ordering of the cation of the ionic liquid about
the nucleophilic nitrogen centre in the starting material was the principal interaction, resulting in an
entropic benefit and an enthalpic cost when compared to acetonitrile. The entropic effect was more
substantial, resulting in an increased rate in the ionic liquid cases. We predicted a similar ionic
liquid effect for the addition reaction between 1 and 2.
O
R = H, OCH3
Acetonitrile
+ H2N
Ionic liquid
R
1
Scheme 5: The addition reaction between benzaldehyde 1 and amine 2 to give the product 3.
The effect that a series of ionic liquids have on the rate constant of this reaction will be
discussed. The ionic liquids used allowed the effect that changing the charge accessibility and
localization on the cation, and the coordinating ability of the anion, to be systematically
investigated. Initially the effect that different mole fractions of ionic liquid in the solvent mixture
have on the rate constant will be covered. The second part involves temperature dependent kinetic
studies to allow calculation of the activation parameters, for each of the ionic liquids used.
Generally it was found that the more localized and available the positive charge on the cation, and
the weaker the coordinating ability of the anion, the larger the enthalpy of activation; suggesting a
greater degree of interaction between the cation and the nitrogen lone pair on the amine 2.
References:
[1] Seddon, K. R., J. Chem. Technol. Biotechnol. 1997, 68, 351; Earle, M. J. et al., Nature 2006, 439, 831.
[2] Keaveney, S. T., Haines, R. S., Harper, J. B., Reactions in ionic liquids. In Encyclopedia of Physical Organic
Chemistry, Wille, U., Ed. Wiley: in press.
[3] Keaveney, S. T.; Harper, J. B., RSC Adv. 2013, 3, 15698; Yau, H. M. et al., Molecules 2009, 14, 2521; Yau, H. M.;
Howe, A. G.; Hook, J. M.; Croft, A. K.; Harper, J. B., Org. Biomol. Chem. 2009, 7, 3572; Tanner, E. E. L.; Yau, H. M.;
Hawker, R. R.; Croft, A. K.; Harper, J. B., Org. Biomol. Chem. 2013, 11, 6170.
M47
Ionic Liquid-Based Mixed Electrolyte for High Performance Rechargeable

Li-O2 Batteries
Asim Khan and Chuan Zhao*
School of Chemistry, The University of New South Wales, Sydney, NSW 2052, Australia
asim.khan@unsw.edu.au, chuan.zhao@unsw.edu.au
Non-aqueous Li-O2 batteries have high specific energy density, however, its commercialization has
been challenged due to several unresolved issues including stability of the electrolyte and
passivation/blocking of the pores of gas diffusive cathode by the reduction products of oxygen
reduction reaction (ORR). The nature of electrolyte plays a critical role in the performance/cycle
life of Li-O2 cell. Decomposition of electrolytes by the attack of reactive reduction products leads to
the formation of lithium alkylcarbonates and lithium carbonate that greatly reduces the
performance/cycle life of Li-O2 batteries [1]. DMSO based Li-O2 batteries have high reversibility
with slight decrease in cell performance [2]. However, recent in-situ studies revealed that DMSO
undergoes anodic oxidation by the reactive oxygen reduction products [3, 4].
Because of their unique properties like non-volatility, non-flammability, thermal stability and good
electrochemical stability, ionic liquids have been considered as an electrolyte for Li-O2 batteries [1].
Ionic liquids have been used to study ORR and can be employed as electrolytes for fuel cell
applications [5]. The addition of ionic liquids into aprotic organic solvent lowers the overpotential
for the oxidation of discharge products and enhances the stability against the attack of superoxide [6,
7]
.
In this presentation, the effect of ionic liquid based mixed electrolytes on the ORR and the
reversibility of oxidation-reduction processes is investigated in the presence of Li+.[8] Compared to
pure DMSO, the ionic liquid based mixed electrolytes exhibit higher conductivity, diffusion and
oxygen solubility. Cyclic voltammetry results show that the mixed electrolyte had better retention
of cathodic current after several cycles than the pure DMSO based electrolyte. The results suggest
that synergetic effects of optimized mixed electrolyte can result in improved cell performance.
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
Black R, Adams B, Nazar LF, Adv. Energy Mater., 2012, 2: 801-815.

Peng Z, Freunberger SA, Chen Y, Bruce PG, Science (Washington, DC, U. S.), 2012, 337: 563-566.
Mozhzhukhina N, Mndez De Leo LP, Calvo EJ, J. Phys. Chem. C, 2013, 117: 18375-18380.
Sharon D, Afri M, Noked M, Garsuch A, Frimer AA, Aurbach D, J. Phys. Chem. Lett., 2013, 4: 3115-3119.
Khan A, Lu X, Aldous L, Zhao C, J. Phys. Chem. C, 2013, 117: 18334-18342.
Cecchetto L, Salomon M, Scrosati B, Croce F, J. Power Sources, 2012, 213: 233-238.
Kim BG, Lee J-N, Lee DJ, Park J-K, Choi JW, Chem. Sus. Chem, 2013, 6: 443-448.
Khan A, Zhao, C, Electrochem. Comm, 2014, accepted
M48
Gibbs monolayer of long-chain ionic liquids: halide-anion effect and monolayer

structure
Woongmo Sunga, Wenije Wangb, Nathaniel A. Andersonb, Ao Mingqia, David Vakninb, and Doseok Kima,*
a
Department of Physics, Sogang University, Seoul 121-742, Korea

Ames Laboratory and Department of Physics, Iowa State University, Ames, Iowa 50011, USA
*doseok@sogang.ac.kr
In aqueous solutions of long-chain ionic liquids, hydrophobic cations are attracted to the air side,
which then facillitates the adsorption of anions to the surface by Coluomb force. This would dictate
that the surface properties like surface excess and critical micelle concentration (cmc) depend on the
cation type (e.g. length of the alkyl chain in the cation) but not on the change of anion. It was
reported, however, that surface tension and cmc of ionic liquid aqueous solutions change with the
change of inorganic anions[1]. Detailed surface structure of the IL+water system will be crucial to
find out the microscopic origin of this phenomenon.
We investigated the composition at the surface and surface structure of the solutions of
alkylimidazolium ionic liquids with different halide anions ([C12mim][X], X = Cl, Br, and I) by
using X-ray reflectivity, X-ray fluorescence, and surface nonlinear-optical spectroscopy. From the
surface tension measurement, it was found that [C12mim]I has the largest surface excess (the
smallest surface area per molecules) indicating that larger and more polarizable I! ion promotes the
surface activity of [C12mim]+. In [C12mim]Cl or [C12mim]I solutions that formed Gibbs monolayer,
inorganic salts having different halide anions were added in the subphase to allow competitive
adsporption. For [C12mim]I solution, adsorbed I! ions were not completely replaced by Cl! even in
bulk NaCl concentration hundred times higher than that of [C12mim]I. On the other hand, a fair
number of Cl! ions were replaced by I! ions when its bulk concentrations is the same as that of
[C12mim]Cl[2]. From grazing incidence X-ray diffraction and sum-frequency generation
spectroscopy, it was found that [C12mim]Cl solution surface exhibits loosely-packed and disordered
monolayer structure whereas [C12mim]I has fully-packed and condensed domains, strongly
suggesting the position of adsorbed halide anions are different between the two ILs.
Figure 1. (a) X-ray reflectivity curve of 20 mM [C12mim]Cl (down triangle), adding 4.2 mM NaI (circle), and adding 20 mM NaI (square). Increment
in reflectivity indicates higher contrast in electron density (b) X-ray fluorescence spectra from Cl- ions integrated below the critical angle (over Qz =
0.01!0.02 !1). The spectrum contains the Cl Ka emission line (~2.6 keV) exclusively. Decrement of intensity indicates substitution of Cl- by I- ions.
References
[1] Dong B, Li N, Zheng L, Yu L, and Inoue T, Langmuir, 2007, 23:4178-4182.
[2] Wenjie Wang W, Sung W, Ao M, Anderson N, Vaknin D, and Kim D, J. Phys. Chem. B, 2013, 117:13884-13892.
M49
Extraction and electroanalytical quantification of capsaicin and ascorbic acid

from fresh chilli using ionic liquids
Benjamin Boon Yuen Lau, Janjira Panchompoo, Leigh Aldous*
Ionic liquids can be used as non-volatile, tunable solvents, extractants and electrolytes.1 This work2
has investigated the ability of various ionic liquids to extract an organic analyte, capsaicin, from
fresh Capsicum annuum Birds eye chilli peppers (also known as Thai chillies), followed by the
electroanalytical quantification of the extracted analyte. Ascorbic acid (Vitamin C) was also
extracted and quantified.
Two ionic liquids were identified to extract capsaicin from fresh chilli more effectively than the
conventional ethanol-based process; the inherently basic 1-ethyl-3-methylimidazolium acetate,
[Emim][OAc], and the inherently acidic 1-ethyl-3-methylimidazolium hydrogen sulfate,
[Emim][HSO4]. These ionic liquids were especially effective due to their ability to extensively
disrupt the biomass (chilli),3 and either protonate or deprotonate the capsaicin and ascorbic acid.
The analytes present in the ionic liquid extracts could be electrochemically quantified using a bare
glassy carbon electrode either in the pure ionic liquid (one pot extraction and quantification) or after
dilution with water/ethanol to assist resolution of the capsaicin (flavour indicator) and ascorbic acid
(freshness indicator) features.
References
1. M. M. Hossain, E. H. B. Anari and L. Aldous, Electrochem. Commun., 2013, 34, 331-334.
2. B. B. Y. Lau, J. Panchompoo and L. Aldous, New J. Chem, 2014, accepted
3. M. M. Hossain and L. Aldous, Aus. J. Chem., 2012, 65, 1465.
T1
Preparation of polyacrylonitrilenatural polymer composite precursors for

carbon fiber using ionic liquid co solvent solutions
Alexis Leblaisa*, Bronwyn Foxa and Nolene Byrnea,
a
Institute for Frontier Materials, Deakin University, Waurn Ponds, Australia

*alexis.leblais@deakin.edu.au
Carbon fiber reinforced composites are rapidly becoming one of the leading materials for
applications that demand lightweight materials with high strength and high stiffness[1,2].
The benefits of using carbon fibers are well documented[3] however, the cost of the precursor and
the environmental footprint of the carbon fiber processing method remains a limiting factor to
widespread use[4].
In this context, we report on the use of ionic liquid co-solvents in the preparation of
polyacrylonitrilenatural polymer carbon fibers as low cost environmentally friendly alternatives to
conventional carbon fibers precursors and processing solvents.
We explored the use of unprocessed cotton and cellulose acetate as low weight percentage, cheap,
additives to blend with PAN. The IL, 1-butyl-3-methylimidazolium chloride, [BMIM]CI was used
as a co-solvent for the dissolution of PAN/cellulose acetate and PAN/raw cotton composite fibres.
We characterized the structure properties of the new composites as a function of dissolving solvent
using solid state NMR, DSC, FTIR and TGA. We showed that the dissolving solvent plays a
significant role in the properties of the new composites and found that the incorporation of the
natural polymer additive impacts the thermal transition temperatures for the PAN.
Figure 1: Electrospun PAN from 30: 70 v/v DMSO: [BMIM]CI into a water bath. Scale 10!m.
References
[1] P. Morgan, Carbon Fibers and their Composites, CRC Press, 2005.
[2] Committee on High Performance Synthetic Fibers for Composites, Commission on Engineering and Technical
Systems, National Research Council , National Academy Press: Washington, 1992.
[3] S. Das, Int. J. Life Cycle Assess., 2011, 16, 268.
[4] L. Scelsi, M. Bonner, A. Hodzic, C. Soutis, C. Wilson, R. Scaife and K. Ridgway, eXPRESS Polym. Lett., 2011, 5.
T2
Synthesis of Highly Luminescent N-doped Carbon Dots Directly from an Ionic

Liquid and Their Catalytic Application
Haitao Lia, Xinyi Zhanga, Douglas R. MacFarlanea*
a
Department of Chemistry, Monash University, Clayton, Victoria, Australia

*douglas.macfarlane@monash.edu
Carbon Dots (C-Dots), a new member of carbon nanomaterials < 10nm wide, have attracted much
attention recently due to their low cost, ready scalability, excellent chemical stability,
biocompatibility and excellent luminescence properties.[1,2] Different methods have been employed
to improve the properties of C-Dots, particularly the doping of other elements into carbon structure.
While partially successful, the synthesis or doping process usually involves complex processes,
expensive precursors, and severe synthetic conditions.[3] Ionic liquids containing Nitrogen atoms
make them important candidates for the precursor of N-Doped carbon materials.[4,5] Herein, we
describe a simple method to synthesize N-doped C-Dots using the DMEDAH ionic liquid (pictured)
as a precursor. The synthesized N-Doped C-Dots can be used as a visible-light controlled acid
photocatalyst for organic synthesis reaction. The use of N-Doped C-Dots as a light responsive and
controllable photocatalyst is a truly novel application of carbon materials, which may significantly
advance research on catalysts for industry, energy and environmental issues.
References
[1] Baker S N, Baker G A, Angew. Chem. Int. Ed., 2010, 49: 6726-6744.
[2] Li H T, He X D, Kang Z H, Huang H, Liu Y, Liu J L, Lian S Y, Tsang C H A, Yang X B, Lee S T, Angew. Chem.
Int. Ed., 2010, 49: 4430-4434.
[3] Li H T, Kang Z H, Liu Y, Lee S-T, J. Mater. Chem., 2012, 22: 24230-24253.
[4] MacFarlane D R, Tachikawa N, Forsyth M, Pringle J M, Howlett P C, Elliott G D, Davis J H, Watanabe M, Simon
P, Angell C A, Energy & Environmental Science, 2014, 7: 232-250.
[5] MacFarlane D R, Forsyth M, Howlett P C, Pringle J M, Sun J, Annat G. Neil W, Izgorodina E I, Acc. Chem. Res.,
2007, 40: 1165-1173.
T3
An Ionic Liquid Lubricant Enables Superlubricity to be Switched on in situ

Using an Electrical Potential
Hua Li,a Ross J. Wood,a Mark W. Rutland,b Rob Atkina*
a

KTH Royal Institute of Technology, SE-100 44 Stockholm, Sweden
Ionic liquids (ILs), which are pure salts that have melting points below 100 C, are promising
candidate lubricants for nanodevices on account of their selective affinity for solid surfaces, high
temperature stability, thermal and electrical conductivity. As ILs are composed solely of cations and
anions, lubricity can be externally controlled in situ by application of a potential to an electrode
surface. The ion composition in the boundary layer responds with the applied potential, and thus
alters lubricity. In this work, the nanotribology of the silica-highly ordered pyrolytic graphite
(HOPG) electrode interface is investigated using atomic force microscopy (AFM). The lubricant is
a IL 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([HMIm] FAP) which is
chemically stable with respect to both air and water. [HMIm] FAP is an excellent lubricant at all
potentials. It binds strongly to the HOPG surface and resists squeeze out. However, at positive
potentials the anion rich boundary layer is superlubricating (friction coefficient < 0.01), and a
frictionless state can literally be switched on.
4.5
4.0
!,-!.,/!!!!!!$"%"&0
Lateral Force (nN)
3.5
3.0
2.5
"!#!!!!!$"%"&'
2.0
(&%"!#!!$"%")"
1.5
(&%*!#!!$"%")"
1.0
+&%"!#!!$"%"&)
0.5
+&%*!#!!$"%""&
0.0
-0.5
-10
10
20
30
40
50
60
70
Figure 1. Lateral force

versus! normal load in air and
in [HMIm] FAP as a function of applied potential for a sharp AFM tip (r !5 nm) sliding on an HOPG surface. The
friction coefficient, !, is extracted from the gradient of the plot when the normal force is higher than 10 nN.
Normal Force (nN)
T4
Synthesis of Novel Sodium-ion Conducting Poly-Ionic Liquid Electrolytes

Jiaye Li,a Maria Forsythb, Michel Armandb and Douglas R MacFarlanea*
a
Monash University, Clayton, Melbourne, Australia
b
Deakin University, Burwood, Melbourne, Australia
jiaye.li@monash.edu
The technology and fundamental research of the sodium-ion battery, unlike its widely used
lithium-ion counterpart, is still in its infancy, despite the fact that sodium is naturally abundant,
environmentally friendly and relatively cheap. As such sodium based systems are ideal for
stationary, large-scale electrical energy storage with lower cost and longer cycle life.[1] Nonetheless,
the safety issue associated with the intrinsic instability of traditional battery electrolytes requires
further attention. To address this, more stable and safer poly-ionic liquid electrolytes are recently
under investigation. In the present study, we describe the synthesis of a novel homopolymer and
copolymers
based
on
the
PSTFSI
poly-anion
(PSTFSI
=
+
poly(styrenesulfonyl(trifluoromethanesulfonyl)imide)) which contains either Na ions alone or a
mixture of Na+ and ionic liquid type cations. Copolymers of PSTFSINa with different ratios of ethyl
acrylate (EA) have also been synthesized, which display 2-3 orders of magnitude higher ionic
conductivity than the PSTFSI based homopolymer systems.
Figure 1. Synthesis of homopolymer (STFSINa) and copolymers (STFSINa-co-EA)

References
[1]
Yuan, S., Huang, X.-L., Ma, D.-L., Wang, H.-G., Meng, F.-Z., Zhang, X.-B., Adv. Mater., 2014, Ahead of
Print. DOI: 10.1002/adma.201304469
T5
SO3H-functionalized Ionic Liquids Catalyzed Direct Dehydrative Coupling of

Alcohols or Alkenes with Alcohols
Feng Han, Zhen Li*, Jing Chen, Chungu Xia*
a
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese
Academy of Sciences, Lanzhou 730000, Peoples Republic of China
* e-mail zhenli@licp.cas.cn and cgxia@licp.cas.cn
Ionic liquids (ILs) are salts being composed of distinct cations and anions that are capable of
facilely tuning, and whereby can be designed for task-specific applications through smart choice of
the respective cation and/or anion. [1] Based on their unique properties and accomplished
capabilities, various ILs have been extensively investigated. For example, alkane sulfonic acid
group functionalized ionic liquids have been reported offering a new possibility for developing
environmentally friendly acidic catalysts due to a combination of the advantages of liquid acids and
solid acids, e.g. uniform acid sites, stability in water and air, easy separation and reusability.[2]
Nucleophilic substitution reactions of alcohols are among the most powerful tools for the
formation of carbon-carbon bonds. [3] Nowadays, there are several methods to fulfill the
construction of CC bonds. However, toxic metals or strong acids are often unavoidable. [4]
Therefore, a milder, environmentally-friendly catalyst system for direct transformation of alcohols
still remains to be explored. In our continuing effort on developing ionic liquids catalyzed reactions,
[5]
herein, we will discuss our recent progress in C-C bonds construction from direct dehydrative
coupling of alcohols and alcohols or alkenes by using SO3H-functionalized ionic liquid as
metal-free, recyclable, eco-friendly and highly efficient catalysts (Scheme 1).
Scheme 1 SO3H-functionalized ILs catalyzed direct coupling of alcohols or alkenes with alcohols
References
[1] a) Welton T, Chem. Rev. 1999, 99: 2071-2084; b) Prvulescu V I; Hardacre C, Chem. Rev. 2007, 107: 2615-2665; c)
Wasserscheid P; Welton T, Ionic liquids in Synthesis. Wiley-VCH: 2008; d) Giernoth R, Angew. Chem. Int. Ed.
2010, 49: 2834-2839.
[2] Gupta N S, Kad G L, Singh J, Catal. Commun. 2007, 8: 1323-1328.
[3] Emer E, Sinisi R, Capdevila M G, Petruzziello D, De Vincentiis F, Cozzi P G, Eur. J. Org. Chem. 2011, 647-666.
[4] Naredla R R; Klumpp D A, Chem. Rev. 2013, 113: 6905-6948.
[5] a) Yang L, Xu L, Xia C, Synthesis 2009, 1969; b) Han F, Yang L, Li Z, Xia C, Org. Biomol. Chem. 2012, 10:
346-354; c) Han F, Yang L, Li Z, Xia C, Adv. Synth. Catal. 2012, 354: 1052-1060; d) Han F, Yang L, Li Z, Zhao Y, Xia
C, Adv. Synth. Catal. 2014, 356: DOI: 10.1002/adsc.201301150.
T6
Cinnamate-based Photoresponsive Ionic Liquids: Synthesis and Photoresponsive

Properties
Zhiyong Li, Xinxin Liu, Xiaojuan Zhang, Jianji Wang*
Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, Key Laboratory of
Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Henan
Normal University, Xinxiang, Henan 453007, P. R. China
*Jianji Wang: jwang@henannu.edu.cn
Ionic liquids (ILs) have been developed rapidly because of their unique physico-chemical
properties. The particular interest is their highly tunable properties by varying the chemical
structures of the ions comprised.[1] Incorporating ILs with photochromism / photoisomerism
functionality will generate photo-responsive ILs. However, few light-responsive ILs have been
reported up to now,[2] and further development is necessary for in-depth investigation of their
physicochemical properties and enhancement of their performance.
In this work, 20 kinds of cinnamate-based ILs have been synthesized and characterized.
Chemical route for the synthesis of such ILs and chemical structure of their cations and anions are
shown in Scheme 1. The photoresponsive properties of these ILs are investigated in detail, and the
main observations of the present work are as follows.
OH
O
Cl
K2CO3
N
CH2Cl2
O
O
N
+ Cn H2n+1Br
[Cn-cinn-py]Br
BrNCH
n 2n+1
O
O
Br+ LiX
NC H
n 2n+1
cinn-py
X
N
[Cn-cinn-py]X
CnH2n+1
n=4,6,8,10,12,14
X = Tf2N , BF4 , PF6 ,
Scheme 1. Chemical route for the synthesis of cinnamate-based ILs and chemical structure of the ILs.
1. In a given solvent, UV-Vis absorption spectra of these ILs are similar, and chemical structure
of the cations and nature of the anions do not affect the UV-Vis absorption spectra of them.
Photoisomerization of cinnamate-based ILs would be realized under irradiation of a 500W mercury
pressure short arc lamp.
2. At a given IL concentration, increase irradiation time could enhance the photoisomerization
of cinnamate-based ILs, the trans-cis isomerization equilibrium of cinnamate-based ILs completed
at about 30 minutes. Solvent properties have a great effect on the photoisomerization of
cinnamate-based ILs, and the light-induced conversion of [C4-cinn-py]Br decreases in the order:
chloroform > ethanol > dichloromethane > methanol > acetonitrile.
References
[1] N. V. Plechkova, K. R. Seddon, Chem. Soc. Rev., 2008, 37, 123-150.
[2] S. Zhang, S. Liu, Q. Zhang and Y. Deng, Chem. Commun., 2011, 47: 6641-6643
This work was supported financially by the National Natural Science Foundation of China (No.21133009, 21273062).
T7
Carbon Nanotube Supported Ionic Liquids for CO2 Capture

Hanming Liua,b, Junhua Huanga *, Phillip Pendletonb
a
Center for Molecular and Materials Sciences, Sansom Institute, University of South Australia, Adelaide, SA 5000,
Australia
Our previous work has shown that transition metal ion-functionalised ionic liquids (ILs) represent
promising
absorbents
for
CO2
capture.[1]
In
a
Zn(II)
functionalised
bis(trifluoromethanesulfonyl)imide (Tf2N) IL, a CO2 absorption capacity higher than 1:1 (CO2:IL)
stoichiometry can be achieved.[2] However, the addition of transition metal ions into ILs results in a
highly rigid ionic network, attributed to the bridging coordination between the metal ions and the
anions. As a result, the ILs are viscous and the ab/desorption rates are slow.[2]
Herein we demonstrate a new strategy to improve the absorption rate and capacity using
surface-modified carbon nanotubes (CNTs) in Zn (II) functionalised N, N-methy ethyl
imidazolium trafluoroacetate (EMIMTFA) IL. We chose CNTs as supports due to their high
specific surface areas, exceptional chemical stability, tunability for surface modification and
reasonable compatibility with imidazolium based ILs and metal ions[3], expecting that the CNTs
would disrupt the long-range coordination between the metal ions and the anions.
The CNTs were covalently grafted with ethylenediamine and were then mixed with an IL of
Zn(TFA)25EMIMTFA to form homogeneous mixtures. An addition of 9 wt% of
ethylenediamine-modified CNTs was shown to facilitate the 1:1 and 2:1 (CO2:Zn (II))
complexation between CO2 and ILs, achieving a CO2 absorption capacity of 7.5 wt% at 2.5 bar and
40 oC, corresponding to a 2:1 (CO2:IL) stoichiometry. A !1-O (end on) coordination mode[4] is
suggested by the infrared spectra for the CO2 absorption adducts. The support of
ethylenediamine-modified CNTs was shown to enhance sorption kinetics, 7-fold faster than that in
Zn (II) functionalised EMIMTf2N IL. No loss of CO2 sorption capacity was observed within five
absorption/desorption cyclings, indicating a good reversibility. The incorporation of CNTs into IL
systems provides an effective method to improve the ab/desorption rates and to enhance CO2
absorption performance.
References
[1] Huang J, Ruether T, Feron P, Zhang Z, WO2011011830-A1.
[2] Liu H, Huang J, Pendleton P, Energy Procedia, 2011, 4: 59-66.
[3] Liu H, Wang X, Fang P, Wang S, Qi X, Pan C, Xie G, Liew K M, Carbon 2010, 48: 721-729.
[4] Gibson D H, Chem. Rev. (Washington, DC, U S), 1996, 96: 2063-2095.
T8
Electrochemical Formation of Palladium Nanoparticles in

1-Butyl-1-Methylpyrrolidinium Salicylate Ionic Liquid
Nai-Chang Loa, Po-Yu Chena,b*

Department of Medicinal and Applied Chemistry, Kaohsiung Medical University
Kaohsiung City 80708, Taiwan
b
Department of Chemistry, National Sun Yat-sen University, Kaohsiung City 80424, Taiwan
Tel:+886-7-3121101ext.2587. Email: pyc@kmu.edu.tw
a
Abstract
The electrocatalytic oxidation of alcohol on ionic liquid-graphite-Pd nanoparticles composite
electrode (IL-GP-PdNPs) in alkaline solution was investigated in this study. The PdNPs were
prepared by controlled-potential bulk electrolysis at -1.4 V in 1-butyl-1-methylpyrrolidinium
salicyate room temperature ionic liquid (BMP-SAL RTIL); the chemical structure of which is
shown in Fig 1.[1] The PdNPs were characterized with transmission electron microscope (TEM) and
scanning electron microscope (SEM). The electrochemically active surface area (ECSA)[2] of the
IL-GP-PdNPs electrodes was determined based on the reduction wave of Pd oxide in 1 M sodium
hydroxide using cyclic voltammetry (CV). CV and hydrodynamic amperometry (HA) were used for
studying the electrocatalytic oxidation of ethanol at the IL-GP-PbNPs electrodes. The PdNPs
prepared in this study show better electrocatalytic activity toward ethanol oxidation than that of the
commercial catalyst (ETK-Pd/C, 20 wt% at active carbon)3.
Fig 1.Chemical structure of BMP-SAL
Reference
[!"#$
!"#$%&$'&($')*+#$,&$-&($')./+0#$1&$2&($!.#$'&$-&($')*+#$2&$3)45&$')*6&$7$!"#$%$889$:;;<=$
8>?@@A@BC#$
%&"#$ DE+0)#$F&$%&($DE+0)#$G&($G+E+HEI/#$J+I&$2&$,4HK"0*+$L+*K04$!""&%$>;$:;<=$MBCMAMBC9#$
%'"#$ ,"+0#$1&($!E.#$-&($1/+0#$2&($1/+0#$L&#$LN*OIK"O)*6&$'"66.+&$!"#$%$>8=$C@APM&
T9
Phase equilibria study of the binary systems of [BMPYR]-based ionic liquids

Elena Lukoshko*, Urszula Doma!ska
Department of Physical Chemistry, Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664
Warsaw, Poland
*E-mail: elukoshko@ch.pw.edu.pl
Ionic liquids (ILs) are the novel, promising compounds provide an attractive characteristics
for various types of chemical separation processes.
The solubility of two new ionic liquids: 1-butyl-1-methylpyrrolidinium tetracyanoborate
[BMPYR][TCB], and 1-butyl-1-methylpyrrolidinium dicyanamide [BMPYR][DCA] in al"ohols,
aromatic hydrocarbons, thiophene or heptane have been determined at ambient pressure in the
temperature range from (270.15 to 313.15) K by a dynamic method. The liquid-liquid equilibria
with upper critical solution temperatures (UCST) for al"ohols and with lower critical solution
temperatures (LCST) for aromatic hydrocarbons has been observed. The complete miscibility in the
liquid phase was observed for the binary systems {[BMPYR][DCA] + alcohols}. A decrease in the
solubility of ILs in alcohols (or aromatic hydrocarbons) was observed with an increase of the alkyl
chain length of the solvent. The experimental results have been correlated using the NRTL
equation.
The experimental data have been compared to the other systems with [BMPYR]-based ILs.
The influence of anion on the phase behaviour has been discussed.
T10
Activity coefficients at infinite dilution for organic solutes and water in

1-butyl-3-methylpyridinium tricyanomethanide ionic liquid
Elena Lukoshkoa *, Fabrice Muteletb, Urszula Doma!skaa
a
Department of Physical Chemistry, Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664
Warsaw, Poland
b
Laboratoire Ractions et Gnie des Procds, ENSIC, 1 rue Grandville, 54000 Nancy, France
*E-mail: elukoshko@ch.pw.edu.pl
Our work presents results of study of new ionic liquid 1-butyl-3-methylpyridinium

tricyanomethanide [BMPy][TCM].
The activity coefficients at infinite dilution "#13 of organic solutes and water in the ionic
liquid [BMPy][TCM] were determined using gasliquid chromatography in a wide range of
temperature from (318.15-368.15) K. The partial excess molar Gibbs energies ( "G1E,! ), enthalpies
( "H1E,! ), entropies (Tref "S1E,! ), the gasliquid partition coefficients ( K L ) at infinite dilution were
calculated from the experimental " 13! . The selectivities ( S12! ) for different separation process
(desulfurization or denitrogenation) were calculated from " 13! , and compared to literature values for
N-methyl-2-pyrrolidinone (NMP), sulfolane and other similar ILs.
Standard ab initio calculations were performed using the Gaussian 03 program package.
Optimized structure of the most stable conformer of the ionic pair was obtained using DFT 6-311++
(d,p) method. The CHELPG atomic charges on the cations and anions are consistent with the
observed trends in " 13! and provide insight into cation or anion pyridine, thiophene interactions.
T11
Structure-Property Relationship of Glyme-Based Solvate Ionic Liquids

T. Mandai,,* K. Yoshida, S. Terada, S. Tsuzuki, K. Ueno, K. Dokko, and M. Watanabe
Department of Chemistry and Biotechnology, Yokohama National University, Yokohama, Japan
National Institute of Advanced Industrial Science and Technology (AIST), Ibaraki 305-8568, Japan
*Corresponding authors e-mail address: monday@ynu.ac.jp
Solvate ionic liquids (ILs) are a new familiy of ILs where ligand molecules as a third component
strongly coordinate to the cations and/or anions to form robust complex ions.[1] One of the most
representative solvate ILs is glyme-alkali metal salt equimolar complexes. Glymes are oligoethers
having multiple ether-oxygen atoms with relatively high electron donating ability, thus, they
strongly solvate Lewis acidic metal cations. The resulting solvate cations behave as independent
ions despite of incorporating molecular solvents as ligands, and hence, these molten mixtures can
be regarded as solvate ILs. During our studies on diverse glyme-alkali metal salt systems, we found
that the limited combinations of equimolar glymes and alkali-metal salts result in low-melting
complexes behaving like typical aprotic ILs, such as showing high ionic conductivity, chemical and
electrochemical stability, non-flammability, and negligible volatility.[2,3]
For typical aprotic ILs, it is well known that ionion interaction predominates their liquid
structure, i.e. the properties of ILs. In the case of glyme-based solvate ILs, ionion, ionsolvent
(iondipole), and their mutual interactions should be considered. Iondipole interaction between
parent cations and glymes competes with ionion interaction between parent cations and anions,
and this competition strongly affects the structures and properties of the resulting complexes. In this
study, we focus on the structure-property relationship of solvate ILs composed of certain glymes
(triglyme,
G3;
tetraglyme,
G4;
pentaglyme,
G5)
and
alkali-metal
bis(trifluoromethanesulfonyl)amide salts, M[TFSA] (M = Li, Na, K). From phase diagrams,
isothermal stability measurements, and phase-state dependent Raman spectra on a series of
glyme-M[TFSA] mixtures, the structural criteria for classifying these mixtures into solvate ILs were
proposed. X-ray crystallography on certain complexes revealed their solvate structures in the
crystalline state. In addition, the solvate stability and physicochemical properties of the solvate ILs
were examined with respect to the parent-metal size and glyme length (Figure 1).
[Li(G3)1][TFSA]
[Li(G4)1][TFSA]
[Na(G5)1][TFSA]
[K(G5)1][TFSA]
Figure 1. Solvate structures of the selected [M(glyme)1][TFSA] complexes and their linear
sweep voltammograms at 60 C.
References
[1] Angell C, Ansari Y, Zhao Z, F. Faraday Discuss., 2011, 154: 927.
[2] Mandai T, Yoshida K, Ueno K, Dokko K, Watanabe M, Phys. Chem. Chem. Phys., 2014, doi:
10.1039/C4CP00461B.
[3] Mandai T, Nozawa R, Tsuzuki S, Yoshida K, Ueno K, Dokko K, Watanabe M, J. Phys. Chem. B, 2013, 117:
1507215085.
T12
Structural Studies of Nanoscale Organic Hybrid Materials for Carbon

Capture
Samila McDonalda, Vince Craig,b Greg Warr,c Rob Atkina,*
a

The Australian National University, Canberra, Australia
c
Nanoscale Organic Hybrid Materials (NOHMs) are composed of silica nanoparticles densely
tethered by a polymer layer (Figure 1(A)). NOHMs are liquid in the absence of solvent or free
polymer (Figure 1(B)). NOHMs exhibit interesting properties such as negligible vapour pressure,
high stability and their properties can be tuned by changing the nanoparticle type or polymer
type/length.[1] Recent studies have demonstrated that NOHMs have potential as green solvents for
CO2 capture.[2] An understanding of the gas-liquid interface is essential for CO2 capture, but a full
structure-property relationship has not yet been established.[3] In light of this, the air-liquid interface
of NOHMs is elucidated using atomic force microscopy (AFM) (Figure 1(C)) and contact angle
measurements. The effect of silica nanoparticle size and mixtures of NOHMs are investigated.
NOHMs properties are characterised and related to the interfacial structure.
Figure 1: NOHMs exhibit structure at the air-liquid interface. (A) Schematic representation of
NOHMs. (B) Photograph of NOHMs demonstrating their liquid nature at ambient temperatures. (C)
High resolution AFM phase image of NOHMs. The scale bar is 22nm.
References:
1.
2.
3.
Petit, C., et al., The Journal of Physical Chemistry C, 2011. 116(1): p. 516-525.
Lin, K.-Y.A., Park, A-H. A., Environ. Sci. Technol., 2011. 45: p. 6633-6639.
Park, A.-H., RSC Advances, 2014. 4(17): p. 8723-8726.
T13
Low Overpotential Water Oxidation to Generate Hydrogen Peroxide

Ciaran McDonnell-Wortha, Douglas R. MacFarlanea
Monash University, Clayton, Australia
ciaran.mcdonnell-worth@monash.edu
Current methods for generating hydrogen peroxide on a scale that is useful for industrial or research
purposes require off-site facilities and inherently dangerous transportation of hazardous goods. Our
research interest is in producing hydrogen peroxide cleanly via electro-catalysed water splitting.
Evidence was found that suggests that direct oxidation of water to hydrogen peroxide can occur
when ammonium-based electrolytes are used in conjunction with a catalytic MnOx working
electrode in a water oxidation cell[1]. Potentially, electrochemical production of hydrogen peroxide
of this type requires less energy than traditional oxidation pathways and may form part of a stand
alone fuel in an energy storage cycle[2]. However, our understanding of this particular water
oxidation reaction and its connection to the structure of the ions in the electrolyte is limited.
Investigations have been made into the activity of different ions and the pH of the electrolyte in this
reaction that reveal the role of solvent structure in stabilising the hydrogen peroxide. Possible uses
of hydrogen peroxide produced this way have also been investigated including in situ bleaching and
chemical oxidation with H2O2.
References
[1]
[2]
A. Izgorodin, E. Izgorodin, D. R. MacFarlane, Energy & Enviroonmental Science 2012, 5, 9496-9501.

R. S. Disselkamp, International Journal of Hydrogen Energy 2010, 35, 1049-1053.
T14
Nanostructure of Glyme-based Solvate Ionic Liquids at the Graphite Interface

as a Function of Potential
Ben McLean,a Hua Li,a Ross Wood,a, Kazuhide Ueno,b Masayoshi Watanabe,b Greg Warr,c Rob Atkina,*
a
b

Solvate ionic liquids (SILs) are

formed by certain glyme Li salt
complexes, prepared by heating
equimolar mixtures of a glyme and a
Li salt (e.g. LiNO3, LiTFSA etc.)
while stirring. The Li ion is bound
4
by the glyme to form a complex
cation, with the anion coming from
the lithium salt. The resultant SILs
of the form [Li(glyme)]X (in this
study
[Li(G4)]TFSA
and
[Li(G4)]NO3) has physicochemical
properties that are typical of ionic
liquids such as high thermal stability and ionic conductivity as well as a wide electrochemical
potential window,1 though it varies with the anion.2 Atomic Force Microscopy (AFM) force curves
for [Li(G4)]TFSA and [Li(G4)]NO3 on a graphite substrate consist of steps due to the formation of
near surface layers. The width of the steps is equivalent to the size of an ion pair determined from
the liquid density. When a potential is applied to the surface, the number of steps increases,
indicating stronger structure, and the width of the step closest to the surface decreases. At positive
potentials the width of the step nearest the surface is consistent with the size of the anion. At
negative potentials, the step with varies between a size corresponding to that of the complex cation
and a smaller step which could be due to the dissociated lithium ion or glyme.
References
(1) Tamura, T.; Yoshida, K.; Hachida, T.; Tsuchiya, M.; Nakamura, M.; Kazue, Y.; Tachikawa, N.; Dokko, K.;
Watanabe, M. Chemistry Letters 2010, 39, 753
(2) Ueno, K.; Yoshida, K.; Tsuchiya, M.; Tachikawa, N.; Dokko, K.; Watanabe, M. J. Phys. Chem. B 2012, 116,
11323-11331
(3) Hayes, R.; El Abedin, S. Z.; Atkin, R. J. Phys. Chem. B 2009, 113, 70497052
(4) Tsuzuki, S.; Shinoda, W.; Seki, S.; Umebayashi, Y.; Dokko, K.; Watanabe, M. ChemPhysChem 2013, 14,
1993-2001
T15
Solubility Determination in Ionic Liquids Using In-Situ IR

Xianghai Meng, Rui Zhang, Haiyan Liu, Chunming Xu and Zhichang Liu*
State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing, China
*Corresponding author: lzch@cup.edu.cn
Ionic liquids (ILs) can be used as extraction/absorption solvents to seperate or to purify compounds,
or as reaction catalysts. Solubilities of compounds in ILs are important data for engineering design
and industrial application. In-situ infrared (IR) is proved to be a good way to measure the sulobility
in ILs[1,2]. The interactions between solutes and ILs can be observed with the in-situ IR
spectroscopy, and then the directly quantitative results based on solute characteristic peaks intensity
are concluded precisely. The solubilities of various hydrocarbons and heteroatomic compounds in
ionic
liquids
1-ethyl-3-methylimidazolium
methylsulfate
([Emim][MeSO4])
and
1-butyl-3-methylimidazolium chloroaluminate ([Bmim]Cl/AlCl3) were investigated.
Table 1 lists some experimental data. In the IL [Emim][MeSO4], alkanes and cyclealkanes showed
low solubilities (below 0.5 g/100gIL), while aromatics as well as hetroatomic compounds showed
high solubilities. Low carbon alcohols (ethanol, 2-propanol, cyclohaxanol and n-heptanol) and
some nitrogen containing compounds (aniline, pyrrole, quinoline and pyridine) were miscible with
the IL. In the IL [Bmim]Cl/AlCl3, the solubility of aromatics was much higher than that of alkanes.
Normal alkane showed lower solubility than isomery alkane with the same carbon number, and the
solubility decreased with increased carbon number for both normal alkanes and isomery alkanes.
Table 1 Solubility of various solutes in ionic liquids, g/100gIL
in [Emim][MeSO4]
solubility, g/100gIL
solubility, g/100gIL
in [Bmim]Cl/AlCl3
toluene
10.89
n-pentane
4.32
cyclohexanone
26.79
n-hexane
2.38
benzoic acid
42.23
n-heptane
1.50
2-methyl thiophene
20.40
n-octane
1.41
benzothiophene
45.15
i-pentane
4.82
tetrahydrothiophene
7.01
i-hexane
2.85
n-butylamine
20.07
i-octane
1.82
Acknowledgement: Financial support was provided by the National Science Foundation of China
(Grant Nos. 21276275, 21206193, 21036008) and the Program for New Century Excellent Talents
in University of China (No. NCET-12-0970).
References
[1] Li ZC, Meng XH, Zhang R, et al., Study of caprolactam solubility in ionic liquids using in-situ IR, The 2nd National
Congress on Ionic Liquid and Green Process, China, Nov. 27, 2011, Guangzhou, 93.
[2] Cascant M., Kuligowski J., Garrigues S., et al., Talanta, 2011, 85(4): 1721-1729.
T16
GEL-IONIC LIQUID BASED SODIUM ION CONDUCTORS FOR SODIUM

BATTERIES
Siti Aminah Mohd Noora,b, Maria Forsythc and Douglas R MacFarlanea
School of Chemistry, Monash University, Clayton Campus, 3800 Victoria, Australia

Chemistry Department, Centre for Defence Foundation Studies, National Defence University of Malaysia, 57000,
Kuala Lumpur, Malaysia
c
ARC Centre of Excellence for Electromaterials Science (ACES) Institute for Frontier Materials Deakin University,
3125, Victoria, Australia
*Email: aminah.mohd.noor@monash.edu
b
Lithium ion batteries are widely used as power storage for almost all portable electronic devices. A
major drawback of lithium ion batteries is their safety concerns especially when using organic
solvents, which can lead to an explosion hazard [1]. In addition, the enormous demands on available
global lithium resources have raised concerns about sustainability of the supply of lithium. In this
case; sodium secondary batteries have emerged as promising alternatives to lithium batteries due to
their properties such as low cost, natural abundance, non-toxicity and low atomic mass [2].
Previously, we reported sodium bis(trifluoromethylsulfonyl) amide (NaNTf2) electrolyte systems
based on 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl) amide (C4mpyrNTf2) ionic
liquids [3]. It was found that the ionic conductivity of electrolytes reached as high as 8 mS/cm. From
the electrochemical stability analysis by cyclic voltammetry, the deposition of sodium metal begins
at !0.2 V (vs. Na+/Na) and the resultant deposits were able to be oxidized back into the electrolyte
at high efficiency. This finding has driven us to develop gelled sodium electrolytes systems based
on ionic liquids to realize a safe, high performance battery electrolyte with sufficient mechanical
properties. This electrolyte will be a promising candidate for secondary sodium batteries, since it
may overcome the cost and sustainability problems associated with conventional electrolytes, while
still exhibiting good conductivities and stability.
References
[1]
[2]
[3]
Tarascon JM, Armand M, Nature 2001, 414: 359-367.

Ellis BL, Nazar LF, Current Opinion in Solid State and Materials Science 2012,16:168-177.
Mohd Noor SA, Howlett PC, Macfarlane DR, Forsyth M, Electrochim. Acta 2013, 114: 766-771.
T17
Reversible Li-Intercalation into Graphite in Lithium Solvate Ionic Liquids

HeeJoon Moon, Kazuki Yoshida, Ryoichi Tatara, Kazuhide Ueno, Kaoru Dokko, Masayoshi Watanabe*
Department of Chemistry and Biotechnology in Yokohama National University, Yokohama, Japan
*E-mail: mwatanab@ynu.ac.jp
Recently, many researchers have studied ionic liquid (IL)-based electrolytes for large scale power
storage for gird and home or batteries for electric vehicles because of their unique properties such
as low-volatility, non-flammability and electrochemical stability. We are employing glyme-Li salt
molten complexs as an alternative electrolyte, which are prepared by mixing equimolar glyme and
lithium bis(trifluoromethanesulfonyl) amide (Li[TFSA]), becasuse they have similar properties to
those for common ILs. The molten glyme-Li[TFSA] complexes are now named solvate ILs. We
reported that the glyme complexs can are promising electrolytes for lithium-sulfur battereies as well
as 4V class Li-ion batteries. [1-3] In this study, we investigated the reversible Li-intercalation into
graphite in the solvate ILs.
Fig.1 shows cyclic voltammograms for graphite-lithium half cells using mixtures of triglyme
(G3) and Li[TFSA] as the electrolytes. In Fig.1, a reversible redox-curve appeared around 0-0.2V in
the solvate IL [Li(G3)1][TFSA], which does not contain excess glyme. This is indicative of
successful intercalation-deintercalation reactions of Li+ in graphite anode. The formation of
Li-graphite intercalation compounds was further verified by X-ray diffuraction. However, the
anodic peaks decreased with increasing excess glyme and the cathodic peaks shifted to higher
voltage (Fig. 1). Moreover, another sharp peak emerged at 0.6-0.8V, suggesting that irreversible
co-intercalation of [Li(glyme)]+ occurred in the presence of excess glyme [Li(G3)x][TFSA] (x>1).
!
!"%
!"$
!"!
(!"#
)*+*, -
!"#
!! 23 456 78 ' 92: ; < - 9
(!"$
!! 23 456 78 '"= 92: ; < - 9

!! 23 456 78 # 92: ; < - 9
(!"%
!! 23 456 78 $ 92: ; < - 9
(!"&
!"! !"# !"$ !"% !"& '"! '"# '"$ '"% '"& #"!
. / 0 *+*1
Fig.1 Cyclic voltammograms for [Li|[Li(G3)x][TFSA]|graphite] at 60 oC.
References
[1] Tamura T, et al., Chem. Lett ., 2010, 39: 753-755.
[2] Tachikawa N, et al., Chem. Commun., 2011, 47: 8157-8159.
[3] Yoshida K, et al., J. Am. Chem. Soc., 2011, 133: 13121-13129.
Acknowledgment
This work was supported by Advanced Low Carbon Technology Research and Development
Program (ALCA) of the Japan Science and Technology Agency (JST).
T18
Bulk Nanostructure of an Ionic Liquid glycerol mixture

Thomas Murphy,a Silvia Imberti,b Greg Warr,c Rob Atkina,
a
b

STFC, Rutherford Appleton Laboratory, Didcot, UK
The nanostructure of a 50:50 vol.% mixture of glycerol and ethylammonium formate (EAF), a
protic ionic liquid (IL), has been investigated using neutron diffraction and empirical potential
structure refinement (EPSR) fits (Figure 1A). EPSR fits reveal that the mixture is nanostructured.
Electrostatic interactions between IL charge groups leads to the formation of ionic regions. These
solvophobically repel cation alkyl groups which cluster together to form apolar domains. The polar
glycerol molecules are preferentially incorporated into the charged domains, and form hydrogen
bonds with EAF charged groups rather than with other glycerol molecules. Radial distribution
functions reveal that glycerol molecules pack around each other in a fashion similar to that found in
pure glycerol. This suggests that a glycerol channel runs through the ionic domain of EAF. In
Figure 1B polar atoms (all oxygen and nitrogen atoms), EAF alkyl chain carbon atoms and glycerol
carbon atoms have been highlighted to higlight the distinct domains formed in the mixture. The
absence of significant glycerol glycerol hydrogen bonding indicates that glycerol molecules are
able to span the polar domain, bridging EAF charge groups. Glycerol can adopt six distinct
conformations. The distribution of conformers in the EAF mixture is very different to that found in
the pure liquid because hydrogen bonds form with EAF rather than with other glycerol molecules,
which
imparts
different
packing constraints.
(A)
(B)
Figure 1. Snapshot of the fitted bulk structure of a 50:50 vol.% EAF/glycerol mixture equilibrated at 300 K
looking through the front face of the simulation box. (A) shows all atoms (B) Hydrogen atoms are renderd
invisible, all nitrogen and oxygen atoms are rendered blue, EAF alkyl chain carbon atoms are rendered grey and
glycerol carbon atoms are rendered yellow.
T19
Saccharification of Eucalyptus globulus by BmimCl dissolution

Tamara M. Santos, Mercedes Oliet*, M. Virginia Alonso, Juan C. Domnguez, and Francisco Rodriguez
Chemical Engineering Department, Complutense University of Madrid,
Avda. Complutense s/n. 28040 Madrid (Spain).
* E-mail: moliet@quim.ucm.es
Lignocellulose materials have received much attention in last years for their conversion to fuels and
chemicals[1]. For the fuel production, cellulose and hemicellulose depolymerization into
monosaccharides is required[2] . This step of hydrolysis is difficult due to the recalcitrante of
biomass. Ionic liquids have shown as biomass solvents with attractive properties such as negligible
vapour pressure, low melting point, and high thermal stability[3]. Recently, it has been found that
carbohydrate fraction from biomass can be hydrolyzed to its monosaccharides, using inorganic acid
catalysts once dissolved in ionic liquids[4, 5].
The aim of this work is to study the acid saccharification of a hardwood in ionic liquid to reach the
maximum concentration of sugars. For this purpose, a solution of Eucalyptus globulus wood in
ionic liquid 1-butyl-3-methylimidazolium chloride (BmimCl) with 5 % (wt/wt) was preheated at
120 C for 1 h. Then, hydrochloric acid 10 % (wt/wt) was added to this reaction mixture and
hydrolysis at different temperatures (80, 100 and 120 C) was carried out in an orbital shaker for 7
h. The samples were analyzed by HPLC with RI detector to determinate the monosaccharides
concentration.
According to the results, the initial rate of formation of glucose and xylose from cellulose and
hemicellulose increased with increasing temperature. At high temperatures (! 100 C), the
maximum concentrations of these monosaccharides were reached. The highest values of
concentration are 4.5 g/L for glucose and 1.0 g/L for xylose at 100 C. After this point, the sugars
concentration decreased due to dehydratation reactions, which transform them into degradation
products. However, at low temperature (80 C), the maximum of concentration has not been
observed.
Thus, the combination of ionic liquid and acid for hydrolysis of Eucalyptus globulus wood under
mild conditions is suitable. The best operating conditions for achieve the maximum concentration
of glucose and xylose are 3 h and 5 h, respectively, at 100 C.
References
[1] Zhang D, Ong YL, Li Z, Wu JC, Chem. Eng. J., 2012, 181-182: 636-642.
[2] Sievers C, Valenzuela-Olarte MB, Marzialetti T, Musin I, Agrawal PK, Jones CW, Ind. Eng. Chem. Res., 2009, 48:
1277-1286.
[3] Liu CZ, Wang F, Stiles A, Guo C, Appl. Energ., 2012, 92: 406-414.
[4] Enslow KR, Bell T, RSC Advances, 2012, 2: 10028-10036.
[5] Hu X, Xiao Y, Niu K; Zhao Y, Zhang B, Baozhong H, Carbohyd. Polym., 2013, 97: 172-176.
T20
3-Dimensional Nanostructure at the Graphite Protic Ionic Liquid Interface

Aaron Elbourne, Ryan Stefanovic, Rob Atkin and Alister J. Page*
Newcastle Institute for Energy and Resources and Discipline of Chemistry
The University of Newcastle, Callaghan, NSW 2308, Australia
*alister.page@newcastle.edu.au
In situ atomic force microscopy and a novel quantum chemical simulation method[1] are used to
resolve the 3-dimensional nanostructure of bulk n-alkyl ammonium nitrate ionic liquids (ILs)
adsorbed on graphite. Unlike molecular liquids such as water, these bulk ILs are nanostructured.
Ionic liquid nanostructure arises from cohesive interactions between the different parts of the ions,
and consists of distinct polar and non-polar domains. In the presence of a solid substrate, bulk
nanostructure is transformed from a sponge-like phase into one consisting of well defined layers
normal to the surface.[2] The lateral structure of an IL within these layers for a bulk liquid solid
interface has not yet been elucidated at the molecular level. We show here that the lateral structure
at the n-alkylammonium nitrate graphite interface is heterogeneous, and highly ordered. The
propylammonium nitrate graphite interface consists of a well-defined superstructure, in which
propylammonium cations preferentially adsorb along two of the three symmetry axes of the
underlying graphite lattice (Figure 1). This lateral superstructure can be changed and controlled
through tuning pertinent environmental factors, including (1) the presence of a potential, (2) the
molecular structure of the component ions and (3) the thickness of the solid-liquid interface.[3] Such
control poses ramifications for how ILs can be used for applications including lubrication,
capacitive charge storage and electrodeposition.
Figure 1. Heterogeneous lateral structure of the propylammonium nitrate graphite interface.
References
[1] Addicoat M, Fukuoka S, Page, A, Irle, S, J. Comp. Chem., 2013, 34:2591-2600.
[2] Hayes R, Warr G, Atkin R, Phys. Chem. Chem. Phys., 2010, 12:1709-1723.
[3] Castens T, Gustus R, Hfft O, Borisenko N, Endres F, Li H, Wood R, Page A, Atkin R, J. Phys. Chem. C., In press.
T21
Liquid phase behavior of binary mixtures containing ionic liquids and molecular
solvents
Paulina Papisa*, Jerzy Szyd!owskia, Jos M. S.S. Esperanab, Jos N. Canongia Lopesbc and Lus Paulo N. Rebelo b
a
Department of Chemistry, University of Warsaw, !wirki i Wigury 101,02-089 Warsaw, Poland

Instituto de Tecnologia Qumica e Biolgica, Universidade Nova de Lisboa, Av. Repblica, 2780-157 Oeiras, Portugal
c
Centro de Qumica Estrutural, Instituto Superior Tcnico, 1049-001 Lisboa, Portugal
*ppapis@chem.uw.edu.pl
Liquid-liquid equilibria of binary mixtures containing ionic liquids and dihydroxy alcohols
or aminoalcohols has been investigated. All phase diagrams were determined using visual cloud
point method. In the experiment we used different bis(trifluoromethylsulfonyl)imide ionic liquids
and molecular solvents like diols, which possess two hydroxyl groups and aminoalcohols, which
possess one hydroxyl group and one amino group.
The different factors have been investigated to check the miscibility of binary mixtures, like: the
alkyl chain length in the ionic liquids cation, the alkyl chain length in the alcohols, the relative
position of two hydroxyl groups in alcohols and the kind of second group ( hydroxyl or amino) in
the alcohols. For example, if we replace one hydroxyl group for amino in 1,3-propanediol we
obtained better miscible system with [N2112O1][NTf2].
Fig.1. Phase diagrams for [N2112O1][NTf2] with " 1,3-propanediol, # ethanolamine and $
3-amino-1-propanol.
This work is realized within the MPD Programme (MPD/2010/4) of Foundation for Polish Science,
cofinanced from European Union, Regional Development Fund.
T22
The Synthesis of Anionic Metal Complex Ionic Liquids and the Application in
Carbon Dioxide Capture
XING Su-hua, DING Jing, PENG Chang-jun*, LIU Hong-lai
Key Laboratory for Advanced Materials and Department of Chemistry,
East China University of Science and Technology, Shanghai 200237, China
* Corresponding author, E-mail: cjpeng@ecust.edu.cn
A class of metal complex anionic ionic liquids [Bmim][AXn+1] can be synthesized by the same
mole of Imidazole ionic liquid [Bmim]X(X=Cl, Ac) and inorganic salt AXn(A=Fe, Zn) through
one-step method whose density and viscosity are measured at different temperature. The
correlation of density and viscosity can be obtained by classic modelwhich can be applied to
analysis the solubility of carbon dioxide in [Bmim]X and [Bmim][AXn+1]. It can be found that the
density and viscosity of [Bmim]X and [Bmim][AXn+1] decrease as the temperature increases.
Meanwhile, the density of metal complex anionic ionic liquids [Bmim][AXn+1] is much higher
than the density of [Bmim]X. It also can be revealed that the viscosity of [Bmim][ZnCl3] and
[Bmim][ZnAc3] are much higher than the viscosity of conventional ILs [Bmim]X, but the viscosity
of [Bmim][FeCl4] is much lower than the viscosity of [Bmim]Cl. It is concluded that metal complex
anionic ionic liquids [Bmim][AXn+1] perform an excellent ability in absorbing CO2.
% Transmittance
&' ( )( *&- ./+ , 0 $ *
&' ( )( *&+ , *
- ./+ , 0 #
"!!!
#!!!
$!!!
%!!!
-1
Wavenumbers (cm )
Fig.1 FT-IR spectrum of Zn(Ac)2, [Bmim][Ac] and [Bmim][Zn(Ac)3]
n CO2 /n IL (mol/mol)
0.8
:[Bmim][ZnCl3 ]
:[Bmim][Zn(Ac) 3 ]
:[Bmim]Cl
:[Bmim] [Ac]
:[Bmim][FeCl4 ]
0.6
0.4
0.2
0.0
0.0
0.5
1.0
1.5
p (MPa)
Fig.2 The solubilities of CO2 in ionic liquids
T23
Electropolymerized carbazole-containing ionic liquid in the electrochemical

determination of bio-molecules
Kirankumar.Rajendranatha, Po-Yu Chena,b*.
a
Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung City 80708, Taiwan
b
Department of Chemistry, National Sun Yat-sen University, Kaohsiung City 80424, Taiwan
*Corresponding author. Tel.: +886 7 3121101x2587; fax: +886 7 3125339.
E-mail address: pyc@kmu.edu.tw (P.-Y. Chen).
Abstract:
In this study, new polymerizable ionic liquids were synthesized and modified upon conductive
surfaces to enhance the sensitivity and/or selectivity of the electrodes, which were used for
electroanalytical and electrochromic application.
Ionic liquid (ILs) have shown the advantages on electroanalysis if they can be modified on
electrode surface. Electropolymerization might be a good approach for the modification of ILs on
conductive surface. Various carbazole-based ILs (Figure 1) were synthesized in this study and they
were electropolymerized on indium tin oxide (ITO) electrodes by three potentiostatic methods (i.e.,
cyclic voltammetry, potentiostatic electrolysis, and potentiostatic pulse electrolysis) using
N-butyl-N-methylpyrrolidinium bis((trifluoromethyl)sulfonyl)imide (BMP-TFSI) as the
electrolyte[ 1 ]. Electrochemical oxidation of the carbazole pendant units affords a conjugated
polymer network (CPN) film of polycarbazole and the polymer is expected to have good
conductivity on the conducting surface[2]. The electrodes with electropolymerized (ILs) will be used
for the determination of various bio-molecules, such as uric acid (UA). The presence of cationic
imidazolium group on the surface of the material may allow the electrochemical detection with high
sensitivity and selectivity[3].
Figure 1: modification of electrode surface with poly-carbazole based ionic liquid.
Reference:
[1]
D.-X. Zhuang,, P.-Y. Chen, Journal of Electroanalytical Chemistry, 2009, 626: 197200.
Antonio F. Frau, Nicel C. Estillore and Rigoberto C. Advincula, ACS Appl. Mater. Interfaces, 2010, 2: 37263737.
[3]
C.M. Maroneze, Electrochimica Acta 2014, 123: 435440.
[2]
T24
Non-stoichiometric protic ionic liquids for enhanced CO2 absorption

Vijayaraghavan Ranaganthan* and D. R. MacFarlane
School of chemistry, Monash University, Melbourne, Australia
*Email: vijay.ranganthan@monash.edu
!"#$#"%&'
Increasing greenhouse gas emissions, such as CO2, are a cause of concern amongst the scientific
community and hence there is an urgent need to reduce the amount of such gasses in the
atmosphere. Although several technologies are available for the absorption of CO2, the most
commonly used commercial technology is
chemical absorption by aqueous amines[1]
-..+/*"0."1*02/3204+*,2/")56"5057 1*02/3204+*,2/",)*208"
despite being energy intensive[2] and
0."9:;<;=".0,4)*+"05"%&' /)>*?,+")*"'@"A%"7 ;"
/04>),2805"#2*3":-;
expensive. Since aqueous amines are
%"
strongly basic, they can result in corrosion
%!
of equipment, tanks and piping.
$"
Alternative materials are required to avoid
)*+,+-./012345.6#.7.#8
$!
these problems, and a promising group of
)*+,+-./012345.6$.7.#8
#"
)*+,+-./012345.6$9".7.#8
candidates are ionic liquids (ILs). ILs
)*+,+-./012345.6#.7.$8
#!
often have negligible vapour pressure, thus
*:+
"
eliminating the possibility of gaseous
emissions.[3] In the context of CO2
!
!
$!
&!
'!
(!
absorption, ILs require less energy in the
!"()*+,
regeneration step,[4] exhibit little volume
expansion after absorption of CO2 and can be more thermally and chemically stable than traditional
CO2 absorbers. In order to lower the potential cost and molar volume of ILs, we have focused on
protic ionic liquids produced by proton transfer, i.e. by simple mixing an acid and a base. While
protic ILs typically have higher volatility at elevated temperatures, we have found they have a
considerably lower CO2 desorption temperature, hence, avoiding any significant evaporative loss
during the absorption/desorption cycle.[5] In this study, stoichiometric (1:1) and non-stoichiometric
(1:2, 2:1, 2.5:1) mole ratios of diamino protic ionic liquids (with and without water addition) have
been made, characterized and evaluated for CO2 capture. The studies reveal that non-stoichiometric
mixtures (2:1 and 2.5:1) enhance CO2 absorption in contrast to stoichiometric (1:1) mixtures.
References
[1] Jou F. Y, Mather A. E, Otto F. D, Can. J. Chem. Eng., 1995, 73: 140-147.
[2] Astarita G, Savage D. W, Bisio A, Gas treating with chemical solvents, John Wiley & Sons, New York, 1983.
[3] Wilkes J. S, Green Chem., 2002, 4: 73-80
[4] Cadena C, Anthony J. L, Shah J. K, Morrow T. I, Brennecke J. F, Maginn E. J, J. Am. Chem. Soc., 2004, 126: 5300.
[5] Vijayaraghavan R, Pas S. J, Izgorodina E. I, MacFarlane D. R, Phys. Chem. Chem. Phys., 2013, 15: 19994-19999.
T25
Anion Stabilisation by Intra-anionic Hydrogen Bonding for Low Viscosity Ionic

Liquids
Anthony Rosamilia and Junhua Huang.*
Energy Technology, CSIRO, Clayton 3169, Australia.
*Corresponding author: Jewel.Huang@csiro.au
Ionic liquids (ILs) have been of great interest as green solvents owing to their low vapour
pressure, high chemical and thermal stabilities, and low flammability.[1] ILs however are notorious
for possessing higher viscosities compared to molecular solvents. A high viscosity affects
negatively on the mass transfer and engineering circulation. For applications where fast mass
transfer is crutial, (e.g. gas diffusion in gas absorption and separation, and ion transport in
electrolytes), their high viscosity could offset their advantageous properties. To address this issue,
anions that have strong electron withdrawing groups and/or utilise resonance stabilisation are used.
Examples are dicyanimide, tris(perfluoroalkyl)trifluorophosphate, tetrafluoroborate, trifluoroacetate
and bis(trifluoromethanesulfonyl)imide.[1,2] In addition, Abbott and co-workers used intermolecular
hydrogen bonding to stabilise anions to form deep eutectic melts.[3,4]
To further explore viscosity-reducing strategies we report an alternative method of anion
stabilisation by introducing hydrogen bond donors (HBDs) onto the anions. The negative charge on
the anion is stabilised by forming intra-anionic hydrogen bonds. This results in weakened
cation-anion interaction and thus the viscosity is reduced.
The effect of intra-anionic hydrogen bond donation is demonstrated by the comparison of
1-ethyl-3-methylimidazolium (EMIM) 2,6-dihydroxybenzoate and EMIM benzoate (Figure 1).[5]
The incorporation of two intra-anionic hydrogen bonds significantly reduces the viscosity. The
resultant IL also displays a lower glass transition temperature and improved thermal stability. This
work further studies intra-anionic HBDs on various anion structures (e.g. benzoates and
dicarboxylates) and their effect on the physical properties such as viscosity, thermal stability and
glass transition temperature of the ILs.
Using this strategy, the anions that bear useful basic functionalities such as carboxylate can
be derivatised with HBDs to achieve a higer fluidity.
Figure 1: Physical Properties of EMIM Benzoates With and Without Hydrogen Bonding.
Arrows Indicate Hydrogen Bonding.
References
[1] Forsyth S, Pringle J, MacFarlane D, Aust. J. Chem. 2004, 57: 113-119.
[
2] Ignatev N, Welz-Biermann U, Kucheryna A, Bissky G, Willner H, J. Fluorine Chem. 2005, 126: 1150-1159.
[
3] Abbott A, Capper G, Davies D, Rasheed R, Tambyrajah V, Chem. Commun, 2003, 70-71.
[
4] Abbott A, Barron J, Ryder K, Wilson D, Chem. Eur. J. 2007, 13: 6495-6501.
[
5] Himmler S, Knig A, Wasserscheid P, Green Chem., 2007, 9: 935-942.
T26
Magnetic Ionic Liquids Based on Bis(trifluoromethanesulfonyl)imide
Anion
Anthony Rosamiliaa, Hanming Liua, Haitao Zhangb, Lingdi Caoa, b, Suojiang Zhangb, Junhua Huanga,*
a
Institute of Process Engineering, Chinese Academy of Sciences, Beijing, China
Room temperature magnetic ionic liquids have been intriguing in recent years due to their unique
magnetic, electrochromic, and photophysical properties in addition to the advantateous properties
for general ionic liquids.[1] The magnetic ionic liquids have been investigated for extraction and
separation[2-4] that could potentially be regulated by external magnetic field.
Here we report novel magnetic ionic liquids based on the bis(trifluoromethanesulfonyl)imide (Tf2N)
anion. A series of magnetic ionic liquids have been prepared by mixing cobalt(II), copper(II) or
iron(II) salt in the N, N!-ethyl methyl imidazolium (EMIM) ionic liquid bearing the same Tf2Nanion. A high concentration of the metal salts can be dissolved in the ionic liquid at a 1:1 molar
ratio, as both the IL and the salts possess the same anion.[5] These materials show good thermal
stability and wide liquid temperature ranges.
Magnetic properties of these transition metal ion-functionalised ionic liquids have been investigated
by a Quantum Design Physical Property Measurement System (PPMS). Temperature dependent
magnetization curves collected from 2 K to 330 K with an applied external magnetic field of 100
Oe and magnetization loop performed at 300 K indicate that these ionic liquids are paramagnetic at
room temperature range. Interestingly, coercivity of 100 Oe was discovered in the M-H loops
collected at 2 K for ionic liquids containing Fe and Co elements, indicating a weak ferromagnetic
interaction.
We investigated their CO2 absorption for CO2 capture purposes. The magnetic ionic liquids exhibit
high CO2 affinities, displaying CO2 absorption up to six times higher than that of the neat
EMIMTf2N. Infrared and Raman spectroscopy measurements suggest, that the addition of transition
metal ions creates the absorption centres, possibly in a form of M[Tf2N]x-,[6] facilitating the
interaction with CO2 molecules. The results demostrate the expansive utility of magnetic ionic
liquids and reveal exciting opportunities for novel capture processes using magnetic regulation.
References
[1] Hayashi S, Hamaguchi H O, Chem. Lett., 2004, 33: 1590-1591.
[2] Okuno M, Hamaguchi, H O, App. Phys. Lett., 2006, 89: 132506.
[3] Albo J, Santos E, Neves L A, Simeonov S P, Afonso C A M, Crespo J G, Irabien A, Sep. Pur. Tech., 2012,
97:26-33.
[4] Huang J, Ruether T, Feron P, Zhang Z, WO2011011830-A1.
[5] Chiappe C, Malvaldi M, Melai B, Fantini S, Bardi U, Caporali S, Green Chem., 2010, 12: 77-80.
[6] Liu H, Huang J, Pendleton P, Energy Procedia, 2011, 4: 5966.
T27
Phenolate Ionic Liquids for CO2 Post Combustion Capture

Anthony Rosamilia, Guangning Yu, Simon Blacket, Junhua Huang*
Energy Technology, CSIRO, Clayton 3169, Australia.
*Corresponding author: Jewel.Huang@csiro.au
Current carbon capture technology to combat the release of anthropogenic CO2 has been
mainly focusing on using amine solutions as CO2 absorbents. To circumvent problems associated
with amine solutions, such as solvent volatility and degradation, corrosion and high energy demand
for regeneration, ionic liquids (ILs) have been under investigation as a new generation of capture
solvents. This is ascribed to their advantageous properties of negligible volatility, thermal stability
and lower heat capacities compared to aqueous amine solutions.
Promising ionic liquids contain CO2 philic groups, such as amines, amino acids,
heterocyclic bases and phenolates.[1-4] It is well known that phenols can be readily substituted on the
aromatic ring. The variation of aromatic substitution of the phenolate ILs allows their physical
properties and CO2 absorption behaviour to be tuned. Dais group has reported phosphonium
phenolate ILs where CO2 absorption capacity and interaction strength were regulated by the
phenolate substitution.[4]
In this work, we further investigate a series of phenolate ILs having various substitutions
and explore the effect of phenolate ring substitution on the physical properties and CO2 absorption
behaviour. (Figure 1). 1-Ethyl-3-methyl imidazolium (EMIM) and N-butyl-N-methyl pyrrolidinium
(P14) phenolates were readily synthesised with high yield by reacting phenols with EMIM or P14
methylcarbonate.[5] The thermal stability of the ILs increases with decreasing the anionic basicity;
whilst increasing the anionic basicity leads to higher CO2 absorption capacities. The potential of
these phenolate ILs as CO2 capture agents will be discussed.
Figure 1: Phenolate ILs Studied for CO2 Capture.

References
[1] Bates E, Mayton R, Ntai I, Davis J, J. Am. Chem. Soc. 2002, 124: 926927.
[2] Goodrich, B. F.; de la Fuente, J. C.; Gurkan, B. E.; Lopez, Z. K.; Price, E. A.; Huang, Y.; Brennecke, J. F. J. Phys.
Chem. B 2011, 115: 91409150.
[3] Gurkan B, Goodrich B, Mindrup E, Ficke L, Massel M, Seo S, Senftle T, Wu H, Glaser M, Shah J, Maginn E,
Brennecke J, Schneider W, J. Phys. Chem. Lett. 2010, 1: 34943499
[4] Wang C, Luo H, Li H, Zhu X, Yu B, Dai S, Chem. Eur. J. 2012, 18: 2153 2160.
[5] Holbrey J, Rogers R, Shulka S, Wilfred C, Green Chem. 2010, 12: 407-413.
T28
Ionic liquid electrolytes for the efficient recovery of Neodymium from

spent NdFeB magnets
Laura Sanchez a,b, Jenny Pringle a, Cristina Pozo-Gonzaloa, Amal Siriwardanab, Maria Forsytha
a) ARC Centre of Excellence for Electromaterials Science, IFM-Institute for Frontier Materials, Deakin University, 221
Burwood Hwy, Burwood, Victoria 3125, Australia;
b) Materials for Energy and Environment Area. Energy and Environment Division. TECNALIA. Mikeletegi, 2. 20009
San Sebastian. Spain
lsanch@deakin.edu.au/ laura.sanchez@tecnalia.com
There is a growing concern about the availability of rare earths as their use in high
technology devices is increasing and China, the predominant supplier, has limited their
exports to conserve scarce resources and protect the environment. Neodymium (Nd) is
one of the most critical rare earths as it is widely used in permanent magnets and is
present in a number of electronic devices (e.g. motors, electric storage systems, etc).
Taking this into account, the recycling of Nd from used magnets becomes an important
aim, to tackle the availability of this critical metal [1]. However, the processes
developed so far present limitations such as complex multi-stage processes, generation
of high amounts of toxic waste and/or consuming extraordinary amounts of energy,
which hinders their implementation [2].
The use of ionic liquids could constitute an interesting alternative to these
technologies. Room temperature ionic liquids are purely ionic compounds with
melting points below room temperature, that possess interesting physicochemical and
electrochemical properties (e.g. electrochemical stability, high ionic conductivity,
chemical versatility, etc) that make them promising electrolytes for the efficient
electrochemical recovery of Nd.
The objective of our work thus far has been to investigate the suitability of P66614TFSI
ionic liquid for the efficient electrochemical recovery of Nd, present in magnets, at
ambient temperatures. Specifically, our study has been focused on understanding the
Nd electrodeposition reaction from the aforementioned ionic liquid containing
different neodymium salts as source of Nd3+ (e.g. neodymium (III)
bis(trifluoromethanesulfonyl)imide, neodymium (III) triflate and neodymium (III)
chloride) using cyclic voltammetry and chronoamperometry as the main techniques.
References
[1] Critical raw materials for the EU - Report of the Ad-hoc Working Group on defining critical raw materials, July
2010.
[2] Mikiya Tanaka, Tatsuya Oki, Kazuya Koyama, Hirokazu Narita, and Tetsuo Oishi. Handbook on the Physics and
Chemistry of Rare Earths, Vol. 43. Chapter 255. Recycling of Rare Earths from Scrap
T28
Chelato Borate Low Temperature Molten Salts derived from Pyrrolidinium

Borohydride and their Application in Battery Electrolytes
Thomas R!thera*, Justen Bremmellb, Thuy Huynha, Carol Huaa, Graeme Snookb, Tony F. Hollenkampa
a
Commonwealth Scientific and Industrial Research Organisation (CSIRO), Energy Technology, Clayton, Australia
Commonwealth Scientific and Industrial Research Organisation (CSIRO), Process Science and Engineering, Clayton,
Australia
*thomas.ruether@csiro.au
Chelato and open chain borates have received much attention in the past as components in
electrolytes for lithium batteries.[1,2] While most of these borates have been prepared as lithium salts
very few examples e exist where the borate is the anion component of quarternary ammonium low
temperature molten salts; the most prominent example is the bisoxalatoborate (BOB). Typically
such salts are prepared by the common metathesis route. With the aim to explore the potential of
new quarternary ammonium low temperature molten salts composed with chelato borate anions we
demonstrate here that pyrrolidinium tetraborohydride is a versatile template from which to approach
the synthesis of such salts:
A
thus
obtained
pyrrolidinium
salt
containing
the
partially
fluorinated
bis(tetrafluorobutanediolato)borate (FBDB) (1) was investigated in more detail with respect to its
use as a component to formulate improved organic carbonate Li-BAT electrolytes. Apart from
general physicochemical data we present data from symmetrical LiLi cell cycling as well as
cycling data from full cell cycling (LMNO electrolyteLi) with high voltage lithium manganese
nickel oxide cathodes (LMNO). In both cases the electrolyte employed consisted of 10 wt% of
pyrrolidinium bis(tetrafluorobutanediolato)borate in conventional EC/DMC 1.0M LiPF6. In both
cell configurations cycling performance of this formulation was superior to the commercial
standard EC/DMC 1.0M LiPF6 electrolyte.
$("
)*+,-./0123.4.,*562 78-90
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><::2,1::2,6,:*;02?@AB!C3D)@32E2$"F5G23'746/D>H)H!?*2
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[1] Xu W., Angell CA, Electrochem. Solid-State Lett., 2001, 65: E1-E4.
[2] Yamaguchi H, Takahashi H, Kato M, Araib J, J. Electrochem. Soc., 2003, 150: A312-A315.
T30
A Method Based on Molecular Dynamics Simulation to Calculate the Nonlinear

Susceptibility of the Ionic Liquid 3-ethyl-1-methylimidazolium nitrate
Qunfeng Shao, Long Yu, Pengfei Cao, Xiaoping Zhang*
School of Information Science and Engineering, Lanzhou University, Lanzhou, China
*zxp@lzu.edu.cn
Px(C/m2104)
The molecular dynamics simulation and subsequent calculation were carried out to study the
optical nonlinear susceptibility of the imidazolium-based ionic liquid 3-ethyl-1-methylimidazolium
nitrate ([EMIM]NO3), which will supply the theory basis for the research on the ionic liquids
nonlinear optical characteristics.
Firstly the geometrical optimization for the single molecular of [EMIM]NO3 were performed
by use of the Gaussian 09 package and the partial charge of those atoms were derived[1]. Then MD
simulation with DL_POLY 4.05 was performed in a system including 512 ion pairs and the refined
force field parameter [2] was applied. The system was equilibrated at 300K and 1 atm in NPT
ensemble lasting 500ps then the NVT ensemble for another 500 ps. The optimized initial
configures density was 1.1806g/cm3. The MD simulations for the ionic liquid system in an
x-directional external static electrical field ranged from 10V/m to 108 V/m by a logarithmic interval
were performed to obtain the positions of the atoms in different external electrical field. Then the
systems dipole P was calculated respectively for different external electrical field. Then the
dipole-electrical fields amplitude curve (P - E curve) was plotted in following figure.
Ex(V/m)
The nonlinear-regression curve fitting based on a simplified relation Px = ! (1) Ex + ! (2) Ex + ! (3) Ex +!
was carried out and derived that the 1st and 3rd order nonlinear susceptibility were
1.0814 !10-11C2 m/J and 3.512 !10-27 C4 m/J 3 respectively. The optical refractive of [EMIM]NO3 was
derived from the 1st susceptibility from our result was 1.491 that is close to the experimental value
with the deviation of 0.04%. And we found that the 3rd nonlinear susceptibility of [EMIM]NO3
was much larger than benzene and other organic liquid. It could be supposed that the ionic liquid is
a kind of potential liquid nonlinear optics material.
References
[1] Aoun, B., et al., Structure of a Prototypic Ionic Liquid: Ethyl-methylimidazolium Bromide. The Journal of Physical
Chemistry B, 2010. 114(39): p. 12623-12628.
[2] Liu, Z., S. Huang and W. Wang, A Refined Force Field for Molecular Simulation of Imidazolium-Based Ionic
Liquids. The Journal of Physical Chemistry B, 2004. 108(34): p. 12978-12989.
T31
Speciation and coordination of cobalt-chloride-based ionic liquids

Chung-Jui Sua,b, Yi-Ting Hsieha, Mei-Chun Laia, Hsin-Liang Huangc, H. Pual Wangb,d, Ching-Yu Pengd, I-Wen Suna,*
a
Department of Chemistry, National Cheng Kung University, Tainan 70101, Taiwan

Sustainable Environmental Research Center, National Cheng Kung University, Tainan 70101, Taiwan
c
Department of Safety, Health and Enivornmental Engineering, Nation United University, Miao-Li 360, Taiwan
d
Department of Environmental Engineering, National Cheng Kung University, Tainan 70101, Taiwan
*IWSun@mail.ncku.edu.tw
b
The ratio of metallic-chloride-based ionic liquids dominates on the speciaition and coordination of
metal ion and causes various viscosity and electrochemical characterization that are always
interesting to scientists. In this studying we employ matrix-assisted laser desorption/ionization
time-of-flight mass spectrometry (MALDI-TOF-MS) and X-ray absorption spectroscopy (XAS) for
understanding the chemical environment of cobalt in cobalt chloride-1-ethyl-3- methylimidozalium
chloride (CoCl2-EMIC) ionic liquids and CoCl42-, Co2Cl62- and Co3Cl82- are identified in
CoCl2-EMIC with various compositions.
References
[1] Hsieh YT, Lai MC, Huang HL and Sun IW, Electrochimica Acta, 2014, 117:217-223
[2] Ynag JM, Hsieh YT, Zhuang DX and Sun IW, Electrochemistry Communications, 2011, 13:1178-1181
T32
Fabricating nanostructured metals and alloys from Lewis acidic metal-chloride

based ionic liquids
Chung-Jui Sua, Fu-Hwa Yeh, Jia-Ming Yang, Jeng-Kuei Changb, I-Wen Suna,*
a
Department of Chemistry, National Cheng Kung University, Tainan 70101, Taiwan

b
Department of Mechanical Engineering, National Central University, Taiwan
*IWSun@mail.ncku.edu.tw
Lewis acidic ionic liquids, prepared by mixing metal chlorids such as aluminum chloride, zinc
chloride, and cobalt chloride with certain organic chloride such as 1-ethyl-3-methylimidzaolium
chloride, are potential electrolyte for the electrodeposition of the corresponding metals and alloys.
Here we report the electrochemical fabrication of nanoporus Pt, Au, Ag, and Cu as well as nanowire
arrays of Al, ZnNi, FeCoZn, ZnAu, and Co[1-5] from the Lewis acidic ionic liquids without using
template. The morphology and composition of the electrochemical fabricated nanostructures are
affected by the experimental parameters including deposition potential, melt composition
(speciation), and temperature. The diameter of wires and size of nanopores could be varied. For
example,in aluminum chloride-trimethylamine chloride, adjustable aluminum wires are provided by
controlling deposited potential. All materials were characterized with SEM, TEM and XRD to
profile morphology, composition and crystal face.
References
[1] Su CJ, Hsieh YT, Chen CC and Sun IW, Electrochemistry Communications, 2013, 34:170-173
[2] Ynag JM, Hsieh YT, Zhuang DX and Sun IW, Electrochemistry Communications, 2011, 13:1178-1181
[3] Yeh FH, Tai CC, Huang JF and Sun IW, The Journal of Physical Chemistry B, 2006, 110:5315-5222
[4] Hsieh YT, and Sun IW, Chemical Communications, 2014, 50:246-248
[5] Hsieh YT, Lai MC, Huang HL and Sun IW, Electrochimica Acta, 2014, 117:217-223
T33
Structural Effects on the Nanoscale Friction Responses of Protic Ionic Liquids

James Sweeneya, Grant B. Webbera, Mark W. Rutlandb,c, Rob Atkina,*
a
Centre for Advanced Particle Processing and Transport, Newcastle Institute for Energy and Resources, The University
of Newcastle, Callaghan, Australia
b
Surface and Corrosion Science, Department of Chemistry, Royal Institute of Technology, Stockholm, Sweden
c
SP Technical Research Institute of Sweden, Stockholm, Sweden
The effect of ionic liquid (IL) molecular structure on nanoscale friction has been investigated using
colloidal probe Friction Force Microscopy (FFM). The ILs studied were ethylammonium formate
(EAF), ethylammonium nitrate (EAN), propylammonium formate (PAF), propylammonium nitrate
(PAN), dimethylethylammonium formate (DMEAF), and ethanolammonium nitrate (EtAN). ILs
were confined between a silica colloid probe and a mica surface, and the friction force was
measured as a function of normal load for sliding velocities between 10 and 40 !ms!1.
At low normal forces, multiple IL layers are found between the probe and the surface, but at higher
force, in the boundary layer regime, a single ion layer separates the probe and the surface. In the
boundary layer regime energy is dissipated by two main pathways. Firstly, the ionic liquid near the
surface, with the exception of the boundary layer, is expelled from the advancing contact made by
the probe on the surface. This disruption in the interactions between the boundary layer and the near
surface multilayers, leads to energy dissipation and depends on the strength of the attraction
between the boundary and near surface layers,. The second pathway is via rotations and twists of
ions in the boundary layer, primarily associated with the cation terminal methyl group. The friction
coefficient did not vary over the limited range of sliding speeds investigated.
Figure 1. Shear force as a function of normal load for a " 15 !m diameter silica colloidal probe
sliding against a mica surface in several protic ILs at a constant mica surface sliding velocity of 40
!ms!1.
T34
Developing Efficient Thermoelectrochemical Systems with Ferrocene-based

Ionic Liquid Electrolytes
Wuan Xin Teh1, Janjira Panchompoo1, Elham Hosseini Bab Anari1, Jeffrey J. Black1, Mark S. Romano2, Jun Chen2 and
Leigh Aldous1,*
1
2
Intelligent Polymer Research Institute, University of Wollongong, Wollongong, Australia

Temperature separated by an electrolyte can be used to generate electricity with no moving parts
by the thermoelectric (or Seebeck) effect. Key requirements for electrolytes include a suitable
dissolved redox couple and the ability to withstand at least low-grade heat (!120C). ILs have been
demonstrated to be eminently suitable for the latter purpose,[1] but work is still progressing on
development of suitable redox species. One measure of a redox couples performance is the
Seebeck coefficient, the potential difference generated as a function of temperature difference
(measured in mV K-1).
The electrochemistry of the ferrocene ferrocenium[2] and the iodide triiodide[3] redox couples
have both been extensively investigated in ILs. When employed individually in
thermoelectrochemical cells their performance is poor; our measurements in [Emim][NTf2]
recorded Seebeck coefficient values of 0.10 mV K-1 and 0.06 mV K-1 for the two redox couples,
respectively.
When ferrocene derivatives and iodine are mixed they form ferrocenium triiodide ILs. Excitingly,
these ferrocenium triiodide ILs have Seebeck coefficients several times higher than that expected
from the sum of the individual ferrocene and iodine redox couples, demonstrating considerable
synergy. The best system to date, dibutyrylferrocenium triiodide, has a Seebeck coefficient of ca.
1.7 mV K-1, which exceeds that of the most commonly used aqueous system.[4]
This poster will present this data, and further data relating to 18 novel ferrocenium triiodide ionic
liquids.
References:
2. N. Sun, M. Rahman, Y. Qin, M. L. Maxim, H. Rodriguez, R. D. Rogers, Green Chem. 2009, 11, 646.
3. D. Klein-Marcuschamer, B. A. Simmons, H. W. Blanch, Biofuel. Bioprod. Bior., 2011, 5, 562.
T35
Preparation and Properties of Ionic Liquids from Cationic Ruthenocene

Complexes with Trialkoxybenzene Ligands
Takahiro Ueda, Tomoyuki Mochida*
Recently, many new ionic liquids containing metal complexes have

been reported. We have prepared functional ionic liquids comprised
of metallocenium cations and fluorinated anions.[1] Herein, we
report on the preparation and properties of ionic liquids containing
cationic ruthenocene complexes [(C5H5)Ru(trialkoxybenzene)]X
(Fig. 1). The PF6 salts were prepared by reacting
[CpRu(NCCH3)3]PF6 with the corresponding arene ligand. The FSA
( =
b i s ( f l u o r o s u l f o n y l )
amide) salts were prepared by anion exchange of PF6 salts.
Fig. 1. Structural formula

of
ruthenocene-based
ionic liquids (n = 2, 6, 12,
18; X = PF6, FSA).
Most of the salts were white solids, but FSA salts with n = 6 and 12 were colorless liquids at room
temperature. The dependence of the melting points on the alkoxy chain length is shown in Fig. 2.
The melting points were below 100 C, except for the PF6 salt with n = 2. In most cases,
crystallization occurred upon cooling from the melt and did not exhibit glass transitions.
Liquid-crystal phases were not observed.
The crystal structures of the PF6 salts were determined crystallographically. The molecular structure
of the cation in the salt with n = 12 is shown in Fig. 3. Layered structures, in which the alkyl chains
are aligned in a parallel manner, were formed in the salts with long alkoxy chains (n = 12, 18).
However, in the salts with short alkoxy chains (n = 2),whereas the anions and cations were packed.
The structural features are consistent with the melting entropy tendencies.
250
200
Tm ( C)
150
100
50
0
-50
0
10 12 14 16 18 20
Carbon number (n)
Fig. 2. Dependence of the melting points on the

alkoxy chain length (!: PF6 salts, ": FSA salts).
Fig. 3. Molecular structure of the cation in

the crystal of the PF6 salt with n = 12.
References
[1] Inagaki T, Mochida T, Takahashi M, Kanadani C, Saito T, Kuwahara D, Chem. Eur. J., 2012, 18: 6795-6804.
T36
Ionic Effects of Glyme-Li Salt Solvate Ionic Liquids on Performance of

Next Generaion Batteries
Kazuhide Ueno, Jun-Woo Park, Ryoichi Tatara, Hoimin Kwon, Azusa Yamazaki, Toshihiko Mandai, Naoki Tachikawa,
Kaoru Dokko, Masayoshi Watanabe
Department of Chemistry and Biotechnology, Yokohama National University, Japan
Much attention is being paid to high-energy density next generation lithium batteries such as
lithium-air (Li-O2) and lithium-sulfur (Li-S) batteries because their specific energy densities are
much higher than those for commercialized lithium ion batteries.[1] However, many challenges
remain unresolved for practical application. Properties of electrolytes are frequently concerned with
serious issues of these batteries. Undesirable side-reactions between electrolytes and the reduction
products (O2 anion radicals for Li-O2 and polysulfide anions for Li-S cells) occur in some
non-aqueous electrolytes. Dissolution of the active species, volatility, and flammability of
electrolytes have also to be addressed for stable operation of the cells. Therefore, development of
electrolytes is a key to establishing these batteries.
Here we report battery performance of Li-S and Li-O2 cells using equimolar molten mixtures of
Li salt (LiX) and triglyme (G3) or tetraglyme (G4) as electrolyte. Appropriate combination of LiX
and the glymes showed IL-like behavior, and thereby they were classified as solvate ILs, in which
all the glyme solvents participated in the formation of discrete [Li(glyme)1]+ complex cation. In
contrast, uncoordinating glyme molecules were present more or less in other mixtures with strongly
basic anions X. These mixtures were not regarded as the solvate ILs but as ordinal concentrated
solutions.[2] We demonstrate that the electrolyte properties depending on the ionic structure
correlate with the cell performance such as capacity, Coulombic efficiency, and reversibility.
For Li-S cells, solubility of lithium polysulfides into the electrolyte was greatly suppressed in the
solvate ILs whereas a large amount of polysulfides were dissolved in the concentrated solutions.
Thus, stable charge-discharge with high Coulombic efficiency was achieved only with the solvate
IL electrolytes.[3] For Li-O2 cells, chemical stability of the equimolar mixtures was studied in the
presence of O2 anion radicals. We found that some anions in the equimolar mixtures undergo side
reactions with the reduction products of O2 in Li-O2 cells. The solvate ILs with
bis(trifluoromethanesulfonyl)amide anion was probed to be stable, and it allowed reversible O2
reduction/evolution reactions in Li-O2 cell. [4]
References
[1] Bruce P. G, S. A. Freunberger, L. J. Hardwick, and J-M. Tarascon, Nat. Mater., 2012, 11: 19-29.
[2] Ueno K, Yoshida K, Tsuchiya M, Tachikawa N, Dokko K, Watanabe M, J. Phys. Chem. B, 2012, 116, 11323-11331.
[3] Ueno K, Park J-W, Yamazaki A, Mandai T, Dokko K, Watanabe M, J. Phys. Chem. C, 2013, 117: 20509-20516.
[4] Tatara R, Tachikawa N, Kwon H-M, Ueno K, Dokko K, Watanabe M, Chem. Lett., 2013, 42: 1053-1055.
Acknowledgment
This work was supported by ALCA of the Japan Science and Technology Agency (JST) and by RISING project of the
Technology Research Grant Program of the New Energy and Industrial Technology Development Organization (NEDO)
of Japan.
T37
Studies on Ultrasonic Assisted Synthesis of Ionic Liquid Confined Porous Silica

Gel Matrices
Yogendra Lal Vermaa, Rajendra Kumar Singha*, Suresh Chandra b
a
Department of Physics, Banaras Hindu University, Varanasi 221005, India

*Corresponding authors e-mail address: rksingh_17@ rediffmail.com
A series of porous silica matrices have been synthesized using ionic liquid (IL)
1-ethyl-3-methylimidazolium thiocyanate ([EMIM][SCN]) by nonhydrolytic sol-gel method with
and without ultrasonic irradiation during gelation. The properties of IL confined silica gel matrices
so prepared have been studied using N2-sorption measurement (for determining pore parameters),
pulse echo technique (for sound velocity and hence elastic modulus determination), DSC, TGA,
FTIR, TEM, SEM and fluorescence techniques. From the N2- sorption measurement, it has been
found that BET surface area increased (due to creation of pits on the surface caused by ultrasonic
irradiation as shown in Figure 1) while pore volume, average pore size and porosity for
ultrasonicated samples decreased. Elastic modulus of the samples containing IL in silica matrices
has been found to change with IL content. Glass transition temperature and thermal stability of the
IL have been found to increase upon confinement in silica gel matrices. FTIR spectra (experimental
as well as computed) show changes in vibrational bands of IL on confinement in pores of silica
matrices. Particularly, for ultrasonicated samples, the bands related to the imidazolium ring,
aliphatic chain and anion SCN of the IL are found to shift upon confinement. Optimised geometry
of the IL in porous matrix shows interaction of these groups with the oxygen present on silica pore
wall. Fluorescence spectra of samples containing IL shows a shift compared to the bulk IL.
(a)
(b)
400nm
400 nm
Figure 1. SEM images of (a) without ultrasonicated sample and (b) ultrasonicated sample.
T38
Efficient SO2 Capture through Ether-functionalized Pyridinium Ionic Liquids

Jian Wanga,b, Shaojuan Zenga,b, Lu Bai a,b, Suojiang Zhanga, Xiangping Zhanga,*
a
State Beijing Key Laboratory of Ionic Liquids Clean Process, State Key Laboratory of Multiphase Complex Systems,
Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China.
b
School of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China.
* xpzhang@ipe.ac.cn
The increasing emitted SO2 has become major atmospheric pollutants to threaten human health,
global climate, agriculture and building materials. On the other hand, SO2 is useful source as the
intermediates in chemical production, so removal and recovery of SO2 is very important. Some
traditional methods, such as limestone scrubbing, ammonia scrubbing and water absorption, have
been widely used but also had several inherent drawbacks like formation of huge amount of
wastewater and calcium sulfate, which could cause secondary pollution to the environment.[1] Ionic
liquids (ILs) are alternative media for SO2 capture due to their unique properties, including high
thermal stability, negligible vapor pressure, a large liquid range and tunable chemical properties.[2]
Currently, a large number of ILs, especially imidazolium-based ILs, have been extensively reported
on SO2 capture. Compared with imidazolium-based ILs, pyridinium-based ILs are relatively
cheaper, lower toxic and easier biodegrade. Besides, due to the ether group induced into ILs might
increase the SO2 absorption ability,[3] thus, developing ether-functionalized pyridinium-based ILs
would further improve the SO2 capture performance.
In the present work, a series of ether-functionalized pyridinium chloride ILs were synthesized and
the physico-chemical properties including density, viscosity, thermal decomposition temperatures
and glass transition temperature (or melting temperature) were determined. The densities of ILs
increased slightly after uptake of SO2, while the viscosities decreased significantly during the gas
absorption. SO2 absorption capacity in ILs increased with decreasing the temperature and also with
SO2 partial pressure rise. The SO2 gravimetric capacity of ILs reached 1.0 ~ 1.4gSO2gIL-1, which is
relatively higher than the other reported Ils, because of the significant interaction between the
electronegative oxygen atom in the cation and the acid SO2, as well as the presence of a
chloride-sulfur interaction between the chloride anion and SO2. Meanwhile, the reusability of ILs
and SO2/CO2 selectivity were investigated. Finally, the absorption mechanism was also investigated
by FT-IR and NMR spectroscopy, and the result showed that SO2 absorption was a purely physical
process. Due to the simple synthesis, excellent reusability, high SO2/CO2 selectivity and relatively
high SO2 gravimetric capacity, ether-functionalized pyridinium chloride ILs can be potential
candidates for SO2 capture in industry.
References
[1] D. Yang, M. Hou, H. Ning, J. Ma, X. Kang, J. Zhang and B. Han, Chemsuschem, 2013, 6, 1191-1195.
[2]! X. Zhang, X. Zhang, H. Dong, Z. Zhao, S. Zhang and Y. Huang, Energy & Environmental Science, 2012, 5,
6668-6681.
[3] S. Y. Hong, J. Im, J. Palgunadi, S. D. Lee, J. S. Lee, H. S. Kim, M. Cheong and K.-D. Jung, Energy &
Environmental Science, 2011, 4, 1802-1806.
T39
Facile, High-Yielding Synthesis of Pyrrolidinium, Piperidinium, Morpholinium

and 2,3-Dihydro-1H-isoindolinium Ionic Liquids From Secondary Amines
Antony J. Warda, Anthony F. Mastersa, Thomas Maschmeyera*
a
Laboratory of Advanced Catalysis for Sustainability, School of Chemistry F11, University of Sydney, 2006,
AUSTRALIA
High yield and purity ionic liquids from secondary amines can be obtained easily via the microwave
irradiation of equimolar amounts of amine and of an !,"-dibromoalkane (i.e., 1,4-dibromobutane,
1,5-dibromopentane, bis(2-bromoethyl)ether, or !,!#-dibromo-o-xylene) in water in the presence
of K2CO3 followed by anion exchange with lithium bis(trifluoromethanesulfonyl)imide, affording
pyrrolidinum, piperidinium, morpholinium and 2,3-dihydro-1H-isoindolinium ionic liquids,
respectively. A total of 35 examples have been prepared using up to 1 h of irradiation time with
yields in the range of 6495%. Using this methodology, a large number of homologous ionic liquids
can be prepared from a small number of readily available and relatively cheap starting materials.
Analysis (using SWOT1 and the GSK greenness assessment2) of this synthetic method and
comparison with current literature preparations reveals that this new method has significant benefits
across of range of relevant parameters.
R1
X
NH
R2
Br
Br
n
R1
i] H 2O, K 2CO3, MW, 120 oC
ii] LiNTf 2
R2
n = 1, 2
X = O, CH 2
R1
R2
35 EXAMPLES
REACTION TIME: 20-60 min
YIELDS: 64-95%
R1
N
R2
NTf 2
R1
N
N
R2
R1
R2
Scheme 1. The general procedure for the preparation of ionic liquids from secondary amines.
References
1
2
Deetlefs, M.; Seddon, K. R. Green Chem. 2010, 12, 17-30.

Adams, J. P.; Alder, C. M.; Andrews, I.; Bullion, A. M.; Campbell-Crawford, M.; Darcy, M. G.; Hayler, J. D.;
Henderson, R. K.; Oare, C. A.; Pendrak, I.; Redman, A. M.; Shuster, L. E.; Sneddon, H. F.; Walker, M. D.
Green Chem. 2013, 15, 1542-1549.
T40
Deep Desulfurization Using Ionic Liquids For Low Sulfur Liquid Fuel
Kailas L. Wasewar, Swapnil A. Dharaskar, M. N. Varma, D. Z Shende
Advanced Separation and Analytical Laboratory, Department of Chemical Engineering, Visvesvaraya National Institute
of Technology (VNIT) Nagpur - 440010, Maharashtra, INDIA.
* Corresponding authors email: k_wasewar@rediffmail.com dr.kailaswasewar@gmail.com
Now-a-days it is mandatory to provide the low sulfur liquid fuel due to environmental
regulation by various countries for the transportation sector which is the big challenge for
worldwide refineries. In present paper extractive desulfurization using ionic liquids has been
discussed. It is an alternative process for the high energy intensive HDS technology for
deep-desulfurization (less than 50 ppm sulfur). Extractive desulfurization using ionic liquids is
promising technology as almost all ionic liquids reported in the literature are moisture-insensitive,
thermally stable under the distillation conditions, and readily regenerated for reuse. The sulfur in
the liquid fuel can be lowered to desired level by multistage extraction. The removed aromatic
S-containing compounds can be quantitatively recovered during the regeneration and ionic liquid
can be reused. The highest extraction with 77.15% sulfur removal efficiency in a single stage
extraction process was observed. Also the used [Bmim]Cl can be regenerated by re-extraction using
tetrachloro-methane with considerable extraction efficiency. The results suggest that compounds
with higher aromatic !-electron density are the most possible reason that those can be extracted by
ionic liquids. The cation and anion structure and size in the ionic liquids are important parameters
affecting the extraction capacity for aromatic sulfur compounds. Various aspects of the process
have been discussed such as extraction time, fuel to ionic liquid ratio, multistage extraction,
extraction mechanism, and regeneration along with process consideration.
ACKNOWLEDGEMENT
Author gratefully acknowledge for the financial support by the Council of Scientific and
Industrial Research (CSIR) grant number (22(0492)/09/EMR-II), Government of India, India
(Principal Investigator: Dr. Kailas L. Wasewar).
T41
Polymerized ionic liquid as a medium of chemical modified electrodes for

mediated electroanalysis
Guor-Tzo Wei,* Hui-Hsuan Chiu, Che-Hung Liu, Sheng-Huang Wu
Department of Chemistry and Biochemistry, National Chung Cheng University, Chia-Yi, Taiwan
*Corresponding authors e-mail: chegtw@ccu.edu.tw
Ionic liquids (ILs) possess many specific physicochemical properties, such as high ionic
conductivity, high viscosity, negligible vapor pressure, and good thermal stability. So they can be
modified onto the electrode to form a stable electric conductive medium. But in the literature,
IL-modified electrodes have long-term stability problem and require complicated preparation
procedures. If the IL-modified electrode can be fabricated in mass production approach, it will
make the electrodes easily accessible. Furthermore, the composite of polymerization of ionic liquid
should solve the long-term stability problem.
In this research, we took a screen printed carbon electrode (SPCE) and using a drop coating method
to prepare the modified electrode. ILs were coated onto a SPCE surface by mixing two ionic liquid
monomers ([C4VIM][PF6] and [C9(VIM)2][PF6]2). After coating, thermal polymerization was
employed to form a hydrophobic polymerized ionic liquid composite. Then, the polymerized-ionic
liquid screen printed carbon electrode (PIL-SPCE) was used to extract electrochemical mediators,
such as ferricyanide (Fe(CN)63-) , methylene blue, and Ru(bpy)3Cl2. The extraction capability of IL
membrane can immobilize the mediators and then it becomes a mediator modified electrode.
In order to demonstrate the capability of PIL-SPCE, the extraction of Fe(CN)63- to form a
FeCN-PIL-SPCE was examined and the working electrode was employed to study the oxidation of
thioglycolic acid (TGA). With FeCN-PIL-SPCE electrode, Electrocatalytic oxidation of TGA at
0.285 V was observed. In addition, the relative standard deviation of peak current for
electrode-to-electrode (n=4) is less than 5%. Furthermore, flow injection analysis (FIA) is used for
the determination of TGA with FeCN-PIL-SPCE. A linear calibration plot in the range of 10 M-1
mM was obtained with the detection limit of 17.4 nM (S/N = 3). The results show that
FeCN-PIL-SPCE electrode has high sensitivity, low detection limit, good repeatability, and high
stability.
We also used FeCN-PIL-SPCE electrode to detect other thiol compounds (Cysteamine,
2-Mercaptoethanol, Cysteine, 3-mercaptopropionic acid, and Glutathione) and observed
electrocatalytic oxidation signal from these thiol compounds. The preliminary results demonstrate
the advantage and potential of PIL-SPCE electrodes.
T42
The study of protein stability in Protic Ionic Liquids (PILs) and molecular
solvents
Emmy C. Wijayaa,b*, Tamar L. Greavesa, Frances Separovicb, Calum J. Drummonda
a
School of Chemistry, The University of Melbourne, VIC 3010

CSIRO Materials Science and Engineering, Bag 10 Clayton, VIC 3169
*emmy.wijaya@csiro.au
It only takes a small change in the environment (such as pH, temperature or salt concentration) to
completely denature a protein. Once the buried hydrophobic parts of the amino acid chain become
exposed during denaturation or folding, amyloid fibrilization may occur. In vivo, amyloid
fibrilization is associated with various neurological disorders; in vitro, this reduces the shelf life or
storage time of protein-based drugs. Thus, it is of paramount importance to keep proteins in their
native state in order for them to be fully functional. One way is to provide a suitable solvent
environment that retains stability and avoids protein aggregation.
Analogous to hydrophobic effect in water, the solvophobic effect has been known to govern
amphiphile self-assembly in non-aqueous solvents. This work takes a further step of complexity to
investigate the interactions between non-aqueous solvents and proteins, which consist of intricate
hydrophobic and hydrophilic regions.
Ionic Liquids (molten salts at temperature below 100oC) are a class of non-aqueous solvents which
have started to gain a lot of attention in protein studies. They are composed of equimolar amount of
cations and anions, in which their physiochemical properties (i.e., viscosity, surface tension,
conductivity) can be finely tuned by simply changing the cation or anion pair[1]. The dominant
solvent properties that affect the stability of a number of proteins, especially the solvophobic effect,
are being investigated. Various characterisation techniques are being employed to determine both
structural and functional stability of selected proteins in Protic Ionic Liquids (PILs) and a number of
molecular solvents. Differential Scanning Calorimetry studies of protein thermal stability and
Fourier Transform Infrared Spectrometer studies of structural studies have shown both stabilising
and destabilising effects from different non-aqueous solvents.
References
[1] Greaves, T.L.; Drummond, C.J. Chemical Reviews 2007, 108: 206.
T43
Influence of Alkyl Chain Length and Anion Species on Ionic Liquid Structure at the Graphite
Interface as a Function of Applied Potential
Ross J. Wood,a Hua Li,a Frank Endres,b Rob Atkina*
a

Institute of Electrochemistry, Clausthal University of Technology, Arnold-Sommerfeld-Str. 6, 38678
Clausthal-Zellerfeld, Germany
Atomic force microscopy (AFM) force measurements elucidate the effect of cation alkyl chain
length and the anion species on ionic liquid (IL) interfacial structure a highly ordered pyrolytic
graphite (HOPG) surface as a function of potential. Three ILs are examined:
1-hexyl-3-methylimidazolium
tris(pentafluoroethyl)trifluorophosphate
([HMIm]
FAP),
1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([EMIm] FAP), and
1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIm] TFSI). The step-wise
force-distance profiles indicate the ILs adopt a multilayered morphology near the surface, c.f.
Figure 1. When the surfaced is biased positively or negatively vs Pt quasireference electrode, both
the number of steps, and the force required to rupture each step increases, indicating stronger
interfacial structure. At all potentials, push-through forces for [HMIm] FAP are the highest, because
the long alkyl chain results in strong cohesive interactions between cations, leading to well-formed
layers that resist the AFM tip. The most layers are observed for [EMIm] FAP, because the C2 chains
are relatively rigid and the dimensions of the cation and anion are similar, facilitating neat packing.
[EMIm] TFSI has the smallest push-through forces and fewest layers, and thus weakest interfacial
structure. Surface-tip attractive forces are measured for all ILs. At the same potential, the attractions
are strongest for [EMIm] TFSI and the weakest for [HMIm] FAP because the interfacial layers are
better formed for the longer alkyl chain cation. This means interfacial forces are stronger, which
masks the weak attractive forces.
Figure 1. Force versus distance profile for a sharp silica AFM tip (r ! 5 nm) approaching an HOPG surface immersed
in [EMIm] FAP at (a) 0 V and (b) -1.5 V versus a Pt quasireference electrode.
T44
A Novel Brnsted Acidic Heteropolyanion-based Catalyst for Synthesis of

Tributyl Citrate Assisted by Microwave Irradiation
Songxue Shao, Haihong Wu,* Ye Liu, Peng Wu
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry,
East China Normal University, Shanghai, China
*hhwu@chem.ecnu.edu.cn
Tributyl citrate is used as an environment-friendly plasticizer for its good quality and has
tremendous potential in chemical industry. Traditionally, the catalysts used in the synthesis of
tributyl citrate are liquid mineral acids, such as H2SO4, HCl and HF. However, these homogeneous
systems lead to corrosion of equipments, occurrence of side reactions, difficulties in separation and
environmental problems. Although heteropolyacids and solid acids can partly overcome these
problems, they also have other disadvantages, such as low catalytic activity and easy to loss. Ionic
liquids display high conversion and selectivity in esterification as green solvent and catalyst. In
order to increase the catalytic activity and improve catalyst recovery, we design a novel acidic
heteropolyanion-based ionic liquid for the synthesis of tributyl citrate.
O
CH2 COOH
HO C COOH + 3 n-C4H9OH
CH2 COOH
IL Cat.
OH O
O
O
+ 3 H2O
Because the catalytic reactivity can be largely affected by the acidity of the catalyst, we
synthesize a series of ionic liquids which have two alkyl sulfonic acid functional groups to improve
their acidity. The heteropolyanion has a positive effect on the thermal stability and melting point,
which enable the ionic liquids stable under microwave-assisted conditions and make the catalysts
easily recycle. After reaction, the catalysts can be easily recovered by filtration and reused. What is
the most important is that we can obtain good conversion and selectivity with only a 0.15mol%
catalyst amount. Besides, they also exhibited high catalytic activity for other different acids and
alcohols. In this way, we increase the activity of catalyst, shorten the reaction time and recover the
catalyst.
IL:
Cation:
HO3S
H
HO3S
H
SO3H
Anion: PW12O403- , PMo12O403- , SiW12O404-
References
[1] Dong L, He L, Tao G, RSC Adv., 2013, 3:48064813.
[2] Leng Y, JWang J, Zhu R, Angew. Chem. Int. Ed., 2009, 48: 168 171.
[3]Li H, Qiao X, Hua L, ChemCatChem., 2010, 2:1165 1170.
[4] Zhen B, Li S, Jiao Z, Ind. Eng. Chem. Res., 2012, 51:10374!10380.
[5] Duan X, Sun R, Sun Z, Catal. Commun., 2013, 42 : 125128.
T45
SO3H
Adsorption and Diffusivity of CO2 in Phosphonium Ionic Liquid Modified Silica

Jiamei Zhua, b, Feng Xina,b, Junhua Huanga*, Xiaochen Dongb,Hanming Liua
a. Energy Technology, CSIRO, BOX 312, Clayton South, VIC 3169, Australia.
b. School of Chemical Engineering and Technology, China University of Mining & Technology, Xuzhou, Jiangsu
221116, P.R. China
*Corresponding author: jewel.huang@csiro.au
Ionic liquids (ILs) have been under research as novel CO2 separation media due to their relatively
high CO2 affinity. A drawback of ILs is their high viscosity, resulting in slow gas diffusion and
consequently slow gas absorption/desorption rates. [1] To overcome the drawbacks, we covalently
grafted phosphonium based ionic liquids onto porous silica to form Supported Ionic Liquid Phases
(SILP), exploiting the advantages of the low cost and the fast diffusivity of porous materials, in
addition to the thermal and chemical stabilities, low volatility and high CO2 selectivity from IL
phase.[2]
Phosphonium BF4 based ILs were covalently attached onto porous silica through phosphine
nucleophilic displacement and then anion exchange.[3,4] The CO2 ad(b)sorption behaviour for the
bulk phosphonium BF4 ILs, the IL modified and unmodified silicas has been investigated and
compared. The CO2 adsorption isotherms at 273 K indicate that the IL modified silica partially
retains the pore characteristics of the bare silica with a slight CO2 adsorption reduction. The CO2
uptakes at 298, 313 and 333 K increase with increasing pressure and decreasing temperature. An
evaluation of adsorption enthalpies using a Clausius Clapeyron equation indicates that, the
adsorption occurs through a weak chemical bonding between CO2 and the silica surface at a low
CO2 loading at 0.01mmol/g; a physical adsorption then dominates at a higer CO2 loading,
corresponding to an adsorption enthaply at about -19 kJ.mol-1. The homogeneous surface diffusion
model (HSDM) fits the real-time adsorption data well for the modified and unmodified silicas. The
CO2 diffusion coefficients for IL modified silica are level with that of unmodified silica (at a level
of 10-7 - 10-8 m2s-1) and are about two to three orders of magnitude higher than that of neat
phosphonium IL (at a level of 10-10 m2s-1). The IL modified silica exhibits a lower adsorption capacity
for N2, clearly showing that the IL phase notably improves the CO2 sorption selectivity against N2. In
conclusion the gas adsorption through the porous nature of the silica still dominates the sorption
behaviour for the IL modified silica. The coated IL layer performs as a selecting film that allows
CO2 to permeate through to the adsorption sites on the solid materials, but impedes other
undesirable components such as N2.
References
[1] Huang J, Rther T, Aust. J. Chem., 2009, 62: 298-308.
[2] Zhu J, Xin F, Huang J, Dong X, Liu H, Chem Eng J, 2014, 246: 79-87.
[3] Modrogan E, Valkenberg M, Hoelderich W, J. Catal, 2009,261:177-187.
[4] Paun C, Stere C, Coman S, Parvulescu V, Goodrich P, Catal. Today, 2008,131:98-103.
T46
Synthesis and Characterizations of Novel Ether Bridge Based

Dicationic Ionic Liquids
Yung-Che Yena, Kai-Shin Chang, Tzi-Yi Wub, I-Wen Suna*
a
b
National Cheng Kung University, Department of Chemistry, No 1. University Road, Tainan, 70101, Taiwan
National Yunlin University of Science and Technology, Department of Chemical Engineering and Materials,
No. 123 University Road, Douliou, Yunlin, 64002, Taiwan
* iwsun@mail.ncku.edu.tw
In this study, several ehter bridge based dicationic ionic liquids(DILs) were synthesised, including
symmetric and asymmetric DILs. Physicochemical and electrochemical properties of these DILs
were investigated. The symmertic DIL 3,3-(2,2-(ethane-1,2-diylbis(oxy))bis(ehane-2,1-diyl))
bis(1-methyl-1H-imidazol-3-ium) bis(trifluoromethyl sulfonyl) amide([IMOI][TFSI], figure 1a)
showed the lowest viscosity and highest conductivity at room temperature.
Comparing to the DIL with similar structure without ether bridge([IMCI][TFSI], figure 1b), the DIL
with ether group showed lower viscosity and higher conductivity(table 1). This result indicated that
the ether group decreases the viscosity of DILs, which was similar to the result of introducting the
ether goup to the side chain of monocation ionic liquids[1]. Besides, for application of DILs as
electrolyte in lithium ionic battery, the oxygen atom of ether group is expected to improve the
movement of lithium ion, as the function of ether group in polymer electrolytes[2].
Figure 1. Imidazole based dicationic ionic liquid (a)[IMOI][TFSI] (b)[IMCI][TFSI]

Table 1. Viscosity and Conductivity of DILs in figure 1.
Temperature
Cation
Viscosity(cp)
Conductivity(mS/cm)
303K
[IMOI]
[IMCI]
370.4
529.9
1.02
0.68
353K
[IMOI]
[IMCI]
44.0
57.0
3.96
3.17
References
[1] Wu, Tzi-Yi; Su, Shyh-Gang; Lin, Keng-Fu; Sun, I-Wen, Electrochimica Acta, 56(2011) 7278-7278
[2] W.H. Meyer, Adv. Mater., 1998, 10, 439-447
T47
Hydrogen-Bonding Interactions between a Nitrile Functional Ionic Liquid and

Dimethyl Sulfoxide
Yan-Zhen Zheng, Yu Zhou, Zhi-Wu Yu*
Department of Chemistry, Tsinghua University, Beijing, 100084, China
* E-mail: yuzhw@tsinghua.edu.cn
The use of task specific ionic liquids (TSILs) is largely hindered due to their high polarity, large
viscosity and high cost. Using mixtures of TSILs and polar molecular solvents instead of pure
TSILs could be an effective approach to solving these problems. Non-covalent interactions greatly
influence the physical properties of the TSIL-cosolvent mixtures and the key to understand the
modulation effect of the mixture is to investigate the molecular interactions between them.
Nitrile functional ILs can be used as solvents for cobalt-catalyzed cyclotrimerisation reactions. In
this work, the hydrogen-bonding interactions between a nitrile functional TSIL
1-propylnitrile-3-methylimidazolium tetrafluoroborate ([PCNMIM][BF4]) and DMSO have been
investigated by attenuated total reflection (ATR) infrared spectroscopy, hydrogen nuclear magnetic
resonance (1H NMR), and density functional theory (DFT) calculations. Excess infrared
spectroscopy[1],[2] and two-dimensional correlation infrared spectroscopy (2D-COS) were applied to
analyze the infrared spectra.
The main conclusions are: (1) C2H is the main interaction site of the cation in forming
cation-anion, cation-DMSO, [PCNMIM][BF4]DMSO, ion clusters and ion clustersDMSO
complexes. (2) There observed two turning points of the wavenumber shift of !C2H, indicating that
the dilution process can be divided into three stages: from larger ion clusters to smaller ion clusters,
then to ion pairs, and finally to individual ions. When the the mole fraction of DMSO is less than
0.6, only larger ion clusters can be broken into smallar ion clusters. When the mole fraction is
between 0.6 to 0.9, smallar ion clusters can be broken into ion pairs. When the mole fraction is
greater than 0.9, ion pairs can be broken into ions. Introducing a nitrile group into the alkyl chain
does not influence the dilution process in the concentration range compared with
1-butyl-3-methylimidazoliun tetrafluoroborate ([BMIM][BF4]) and DMSO system.[3] (3) The
hydrogen-bonds of the aromatic CHs in [PCNMIM]+ are strengthened in the dilution process while
those of the alkyl CHs and C!N of [PCNMIM]+ are weakened. (4) The cation can work as an
electron donor using the electron rich nitrile group, and in the mean time it can also work as an
electron acceptor using the electron lacking group such as aromatic hydrogen atoms. This could be
the reason that nitrile functional ILs can be used as solvents for cobalt-catalyzed cyclotrimerisation
reactions. (5) The cation did not form micelle or other larger aggregates in the mixture.
References
[1] Li Q Z, Wu G S, Yu Z W, J. Am. Chem. Soc., 2006, 128: 14381439.
[2] Li Q Z, Wang N N, Zhou Q, Sun S Q, Yu Z W, Appl. Spectrosc., 2008, 62: 166170.
[3] Zheng Y Z, He H Y, Zhou Y, Yu Z W, J. Mol. Struct., DOI: 10.1016/j.molstruc.2014.01.013.
T48
Synthesis, Properties and Applications of Chiral Amino Acid Ionic Liquids

(CAAILs) based on Triaminocyclopropenium Salts
Owen J. Curnow* and Ruhamah Yunis
* E-mail: owen.curnow@canterbury.ac.nz
Triaminocyclopropenium salts have been found to have remarkably high thermal stabilities as well
as being stable to a wide variety of chemical environments[1]. Chiral amino acid ionic liquids
(CAAILs) based on triaminocyclopropenium salts can be readily prepared in good yields by
reaction of an easily accessible alkoxydiaminocyclopropenium salt with an amino acid[2]. The
methylsulfate anion can be readily exchanged for other anions.
In this poster, we will describe the properties of these CAAILs: TGA, DSC, viscosity, and
miscibility/solubility. The contribution of the zwitterionic form of the CAAIL was found to be
anion dependent and this will also be discussed. Their potential as chiral discrimination reagents
was trialled as well as their use in aldol and Diels-Alder reactions.
References
[2] Curnow OJ, Holmes MT, Ratten LC, Walst KJ, Yunis R, RSC Adv., 2012, 2: 1079410797.
T49
Hydrolysis of cyclohexanone oxime in SO3H-functional ionic liquid

Yuanyuan Xu, Zhihui Li, Dongsheng Zhang *, Shufang Wang, Xinqiang Zhao, Yanji Wang *
Key Laboratory of Green Chemical Technology & High Efficient Energy Saving of Hebei Province, School of Chemical
Engineering, Hebei University of Technology, Tianjin, 300130, PR China
* zds1301@hebut.edu.cn (D. Zhang), yjwang@hebut.edu.cn (Y. Wang)
Oximes are useful derivatives of carbonyl compounds. These are frequently used for protecting
carbonyl group in organic synthesis [1], which serves as purification and characterization of
carbonyl compounds. Hence it is important for regeneration of the parent carbonyl compounds from
oximes [2]. Curently there are a good number of deoximation methods based on hydrolytic,
reductive, oxidative and transoximation reactions [3]. Among them, acid hydrolysis is one of the
effective method. However, it usually involves strong inorangic acidic conditions. Recently it was
reported that the reaction could be achieved in supercritical water [4]. But it required relatively harsh
conditions. More recently metal chloride ionic liquids (ILs) was successfully used as a catalyst [5].
However, water content in the reaction system has a great influence on the hydrolysis. It is very
strange that no water was straightly added into the reaction system; otherwise the hydrolysis was
totally quenched. Therefore, SO3H-functional ILs were prepared and used in the hydrolysis of
cyclohexanone oxime.
The ILs were synthesized according to previous literature [6]. The hydrolysis reaction was performed
in a 100 ml three-necked flask. Typically, cyclohexanone oxime, ionic liquid and water was added
into the flask. The reaction mixture was heated to 60 C and kept for 1 h. Then the resulting mixture
was cooled, and extracted three times with toluene. The organic phase was identified and analyzed
by a SP-3420 gas chromatography. The obtained ILs aqueous solution was evaporated in a rotating
vacuum evaporator to remove water. The recovered ILs was obtained for catalytic testing.
Various reaction parameters such as reaction temperature, time, the amount of ionic liquid and
water were optimized. The results showed that [HSO3-bmim][HSO4] ionic liquid has a good
performance for the present reaction. Interestingly, the hydrolysis would not proceed without
adding water. Only adding a small amount of water, the reaction would takes place. It means water
is an essential component for the hydrolysis. The optimized reaction conditions investigated were
the molar ratio of IL:cyclohexanone (molar ratio) 4~6:1, conducted at 60 C for 1 h. Nearly 100%
of cyclohexanone oxime was converted to cyclohexanone. Recycling experiments suggested that
the conversion of cyclohexanone oxime was still high than 90% as the catalyst was used for the
third time. It indicates that the ILs catalytst was stable enough to be recycled for the hydrolysis.
References
[1] Sahu S, Sahu S, Patel S, Dash S, Mishr BK, Indian. J. Chem., 2008, 47B: 259-271.
[2] Li z, Ding R, Xing Y, Shi S, Synthetic Commun., 2005, 35: 2515-2520.
[3] Lin M, Liu H, Chang C , Lin W, Chuang T, Molecules., 2012, 17: 2464-2473.
[4] Ikushima Y, Hatakeda K, Sato O, Yokoyama T, Arai M. J. Am. Chem. Soc., 2000, 122: 1908-1918.
[5] Zhang X , Lu B , Wang X , Zhao J , Cai Q , Chin. J. Chem., 2011, 29: 1846-1850.
[6] Duan Z, Gu Y, Zhang J, Zhu L, Deng Y, J. Mol. Catal. A: Chem., 2006, 250: 163-168.
T50
CFD simulation on mass transfer properties of CO2 bubbles in ionic liquids

Di Baoa,b, Xin Zhanga,b, Xiangping Zhangb, Suojiang Zhangb
a
College of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences, Beijing, 100049, China
Beijing Key Laboratory of Ionic Liquids Clean Process, State Key Laboratory of Multiphase Complex System, Institute
Abstract
As potential green solvents, ionic liquids (ILs) exhibit an excellent performance on gas separation,
especially on CO2 capture, due to their low vapor pressure, high thermal stability and high CO2
solubility. However, high viscosity and low CO2 diffusivity in most ionic liquids lead to high
resistance of the gas-liquid flow and mass transfer. Nevertheless, CO2 dissolved in ILs usually
causes decrease of liquid viscosity when the absorption is physically dominated[1], which makes the
mass transfer process in IL-CO2 systems more complex. Therefore, the bubble behavior[2] and mass
transfer properties of CO2 in ILs are critically important for the development of new CO2 capture
process.
In this work, the key effect factors of pressure, temperature, water content and bubble coalescence
on CO2 mass transfer rate and flux in pure ILs ([bmim][BF4], [omim][BF4], [bmim][NO3]) and
aqueous [bmim][BF4] were investigated. A new mass transfer model is proposed to describe the
bubble behavior and mass transfer properties in IL-CO2 systems. Considering the liquid viscosity
change caused by interfacial mass transfer in IL systems, the proposed model was improved with
the modification of experimental mass transfer coefficients of ILs. The simulation results of bubble
diameter and velocity were compared with the experiment results[3] to validate the hydrodynamics
models. Moreover, the CO2 concentration distribution was predicted by the computational fluid
dynamics (CFD) simulation, which provides important parameters for industrial design of ILs-CO2
system.
References
[1] Ahosseini A, Ortega E, Sensenich B, Fluid Phase Equilibr., 2009, 286: 62-68.
[2] Zhang X, Dong H, Huang Y, Chem. Eng. J., 2012, 209: 607-615.
[3] Zhang X, Dong H, Bao D, Ind. Eng. Chem. Res., 2014, 53: 428-439.
T51
Efficient SO2 Capture through Ether-functionalized Pyridinium Ionic Liquids

Jian Wanga,b, Shaojuan Zenga,b, Lu Bai a,b, Suojiang Zhanga, Xiangping Zhanga,*
a
State Beijing Key Laboratory of Ionic Liquids Clean Process, State Key Laboratory of Multiphase Complex Systems,
Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China.
b
School of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China.
* xpzhang@ipe.ac.cn
The increasing emitted SO2 has become major atmospheric pollutants to threaten human health,
global climate, agriculture and building materials. On the other hand, SO2 is useful source as the
intermediates in chemical production, so removal and recovery of SO2 is very important. Some
traditional methods, such as limestone scrubbing, ammonia scrubbing and water absorption, have
been widely used but also had several inherent drawbacks like formation of huge amount of
wastewater and calcium sulfate, which could cause secondary pollution to the environment.[1] Ionic
liquids (ILs) are alternative media for SO2 capture due to their unique properties, including high
thermal stability, negligible vapor pressure, a large liquid range and tunable chemical properties.[2]
Currently, a large number of ILs, especially imidazolium-based ILs, have been extensively reported
on SO2 capture. Compared with imidazolium-based ILs, pyridinium-based ILs are relatively
cheaper, lower toxic and easier biodegrade. Besides, due to the ether group induced into ILs might
increase the SO2 absorption ability,[3] thus, developing ether-functionalized pyridinium-based ILs
would further improve the SO2 capture performance.
In the present work, a series of ether-functionalized pyridinium chloride ILs were synthesized and
the physico-chemical properties including density, viscosity, thermal decomposition temperatures
and glass transition temperature (or melting temperature) were determined. The densities of ILs
increased slightly after uptake of SO2, while the viscosities decreased significantly during the gas
absorption. SO2 absorption capacity in ILs increased with decreasing the temperature and also with
SO2 partial pressure rise. The SO2 gravimetric capacity of ILs reached 1.0 ~ 1.4gSO2gIL-1, which is
relatively higher than the other reported Ils, because of the significant interaction between the
electronegative oxygen atom in the cation and the acid SO2, as well as the presence of a
chloride-sulfur interaction between the chloride anion and SO2. Meanwhile, the reusability of ILs
and SO2/CO2 selectivity were investigated. Finally, the absorption mechanism was also investigated
by FT-IR and NMR spectroscopy, and the result showed that SO2 absorption was a purely physical
process. Due to the simple synthesis, excellent reusability, high SO2/CO2 selectivity and relatively
high SO2 gravimetric capacity, ether-functionalized pyridinium chloride ILs can be potential
candidates for SO2 capture in industry.
References
[1] D. Yang, M. Hou, H. Ning, J. Ma, X. Kang, J. Zhang and B. Han, Chemsuschem, 2013, 6, 1191-1195.
[2]! X. Zhang, X. Zhang, H. Dong, Z. Zhao, S. Zhang and Y. Huang, Energy & Environmental Science, 2012, 5,
6668-6681.
[3] S. Y. Hong, J. Im, J. Palgunadi, S. D. Lee, J. S. Lee, H. S. Kim, M. Cheong and K.-D. Jung, Energy &
Environmental Science, 2011, 4, 1802-1806.
T52
Techno-Environmental Analysis of Ionic Liquids Scrubbing processes for Biogas

Upgrading
Yajing XU, Ying HUANG, Xiangping ZHANG, Suojiang ZHANG
Beijing Key Laboratory of Ionic Liquids Clean Process, State Key Laboratory of Multiphase Complex Systems, Institute
Biogas upgrading aiming at removing CO2 and other trace impurities from the raw biogas is a
necessary step before the biogas being used on a large scale and commercialization. As a promising
absorbent, ionic liquids (ILs) have attracted much attention due to their negligible vapor pressure
with potentials of lower regeneration energy consumption and solvent losses. Although various CO2
capture performances from flue gas by pure ILs have been reported, the studies referring to biogas
upgrading by ILs are quite few. In this work, we developed three kinds of ILs as physical
absorbents employed in biogas upgrading and evaluated their separation performance by simulation
approaches.
The results of IL-based systems were compared with Pressured Water Scrubbing (PWS) and
monoethanolamine (MEA) aqueous scrubbing (MAS) respectively with respect to the energy
consumption and environmental impacts.
Thermodynamic models are the core of simulation and design of a process and suitable models
will make the simulation results closing to the real process. Due to the shortage of parameters
related to the IL-based systems, we measured the vapor-liquid phase equilibria (VLE) of CO2/ILs
and CH4/ILs. The physical properties of ILs were estimated by FC-CS model[1], and PR equation of
state was adopted for designing the thermodynamic models of VLE of capture system and the
parameters were regressed based on the experimental data. The predicted values showed a good
agreement with the experimental ones. The various IL-based biogas upgrading systems were
assessed in terms of their energy consumption and environmental impacts, while CH4 recovery
ratio, specific energy consumption, energy efficiency and Green Degree[2] are calculated as
assessment indicators. The results showed that IL-based systems required lower energy demand
compared with MEA system, and also produced lower environmental impacts. This work provides
important information to choose and develop suitable biogas upgrading technologies.
References
[1] Huang Y, Dong H, Zhang X, Li C, Zhang S. AIChE J, 2013, 59: 1348-59.
[2] Zhang X, Li C, Fu C, Zhang S. Ind. Eng. Chem. Res., 2008, 47: 1085-94.
T53
Stability of Solvates and Electrochemical Properties of Solvate Ionic Liquids

Ce Zhang, Azusa Yamazaki, Junichi Murai, Kazuhide Ueno, Kaoru Dokko, and Masayoshi Watanabe*
Department of Chemistry and Biotechnology, Yokohama National University
79-5 Tokiwadai, Hodogaya-ku, Yokohama 204-8501, Japan
*Corresponding authors e-mail address: mwatanab@ynu.ac.jp
Solvate ionic liquids are a new class of room-temperature ionic liquids (ILs) in which ligand
molecules, as a third component of the liquids, strongly solvate the cations and/or anions of salts to
form complex ions. The lithium solvate ILs exhibit many desirable properties as a
lithium-conducting electrolyte, including high lithium transference numbers, high Li+ ion
concentration, and improved oxidative stability, in addition to commonly observed features of ILs
such as low vapor pressure and high thermal stability.[1,2] These characteristics allowed the
successful operation of lithium ion batteries with various cathode and anode materials.[3,4]
To develop a basic understanding of solvate ILs and their unique properties, we investigate a
structurally related series of concentrated mixtures of Li[TFSA] and oligoether solvents to clarify
the effect of ion-dipole (or ion-induced dipole) interactions on the formation of solvate ILs.
Whereas G3 and G4 possess 4 and 5 coordination sites, respectively, in each molecule to chelate the
Li+ ion, the number of oxygen atoms per molecule becomes smaller for diglyme (G2), monoglyme
(G1), and tetrahydrofuran (THF). Furthermore, the physicochemical properties of the concentrated
mixtures were explored at a constant [O]/[Li+] ratio of 4, and compared with those for the
previously reported typical solvate ILs [Li(G3)1][TFSA].
The oxidative stability of molten solvates of [Li(glyme or THF)x][TFSA] ([O]/[Li] = 4) changes
depending on the structural stability of [Li(glyme or THF)x]+; for instance, complex cation
[Li(G3)1]+ with tetradentate ligands is rather stable owing to the chelate effect, compared with
[Li(G1)2]+ and [Li(THF)4]+. The performance of Li-LiCoO2 cells is affected significantly by the
oxidative stability of the electrolytes. The cell with [Li(G3)1][TFSA] electrolyte showed a good
cycle stability with a high Coulombic efficiency, while the degradation of performance due to the
oxidative decomposition of the solvents was observed for the cells with [Li(THF)4][TFSA] and
[Li(G1)2][TFSA]. In addition to the oxidative stability, the corrosion of the Al current collector is
also affected by the structural stability of [Li(glyme or THF)x][TFSA]. The rate of corrosion
reaction, studied by cyclic voltammetry and SEM observation of the Al electrode, indicates that in
[Li(THF)4][TFSA] and [Li(G1)2][TFSA] is much faster than that in [Li(G3)1][TFSA], and
consequently the corrosion of Al current collector in Li-LiCoO2 cell causes the fade of discharge
capacity and the low Coulombic efficiency of charge-discharge of the cell.
References
[1] Tamura T, Yoshida K, Hachida T, Tsuchiya M, Nakamura M, Kazue Y, Tachikawa N, Dokko K, Watanabe M,
Chem. Lett. 2010, 39: 753-755.
[2] Yoshida K, Nakamura M, Kazue Y, Tachikawa N, Tsuzuki S, Seki S, Dokko K, Watanabe M, J. Am. Chem. Soc.
2011, 133: 13121-13129.
[3] Seki S, Takei K, Miyashiro H, Watanabe M, J. Electrochem. Soc. 2011, 158: A769-A774.
[4] Orita A, Kamijima K, Yoshida M, Dokko K, Watanabe M, J. Power Sources 2011, 196: 3874-3880.
T54
Response of a new multi-walled carbon nanotubes modified carbon paste

electrode to 1-hexyl-3-methylimidazolium cation in aqueous solutions
Hao Rena, Chunfeng Wanga, Xueli Maa, Yujuan Chena, Kelei Zhuoa,*
a
Henan Normal University, Xinxiang, Henan, Peoples Republic of China

* E-mail addresses: klzhuo@263.net, kzhuo@htu.cn
Ionic liquids (ILs) are considered as a class of promising and green non-molecular solvents
in many processes owing to their unique chemical and physical properties. Recently, it has been
demonstrated that many commonly used ionic liquids have a certain level of toxicity.[1] Therefore, it
is desired to develop a simple, effective, and environment-friendly method for the determination of
these ILs in environmental and biological samples. The interest in ion-selective electrodes (ISEs)
has grown over recent years as they are easy-to-use devices that allow rapid and accurate analytical
determination of chemical species at relatively low concentration, with a reasonable selectivity and
low cost. To the best of our knowledge, there are rarely reports on the utilization of ISEs in the
determination of ILs in solution in the literature.[2,3]
In our previous work,[3] a new PVC membrane electrode was made for determination of the
1-alkyl-3-methylimidazolium bromide ionic liquids ([Cnmim]Br, n = 3 8). However, the main
problem of PVC membrane ion-selective electrode is their low physical and mechanical stability
after a series of experiments. In order to improve the performance of electrode and overcome the
low physical and mechanical stability, a new MWCNTs/Nano-silica/CPE was prepared. The
MWCNTs/Nano-silica /CPE could be used for long term and renewed easily by mechanical
polishing whenever needed. The proposed electrode exhibited the Nernstian response to
1-hexyl-3-methylimidazolium bromide ionic liquid (Fig. 1). The as-prepared MWCNTs/Nano-silica
/CPE was successfully applied in the detection of [C6mim]+ in distilled water, tap water and river
water with satisfactory results.
350
2
R =0.998
E/mV
300
250
200
150
1
-log(m/m0 )
Fig. 1. The calibration curve of the MWCNTs/Nano-silica/CPE based on [C6mim]-TPB
Acknowledgement: Financial supports from the National Natural Science Foundation of China
(Nos. 20973055, 21173070) and the Plan for Scientific Innovation Talent of Henan Province (No.
124200510014) are gratefully acknowledged.
References
[1] Zhao D, Liao Y, Zhang Z, CLEANSoil, Air, Water, 2007, 35: 42-48.
[2] Ortuo J, Cuartero M, Garca M, Albero M, Electrochimica Acta., 2010, 55: 5598-5603.
[3] Zhuo K, Wei Y, Ma J, Chen Y, Bai G, Sensors and Actuators B: Chemical., 2013, 186: 461-465.
T55

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th

The 4 Asia-Pacific Conference on Ionic

Sydney, Australia 2014

Local Organising Committee

International Advisory Committee

Conference Programme at a Glance

Conference Programme at a Glance

Conference Programme at a Glance

Conference Programme at a Glance

The Ian Potter Foundation

Io-Li-Tec, Ionic Liquid Technologies

ProDigital Pty. Ltd.

ARC Centre for Excellence for Electromaterials Science

Getting to and from Coogee

Poster Presentations - Monday 29th September

University of New South

Biomass Processing of Rice Husks with Partially Hydrated

Increasing the efficiency of ionic liquid-based

University of New South

Electrodeposition of Pd-Sn Alloy Catalyst from Ionic Liquids

San Mei Bong

Bioethanol production from lignocellulose materials via the

Compartmentalisation by Vesicles in Ionic Liquids

University of New South

The effect of ionic liquids on reactions at phosphorus

Electrochemistry of ionic liquids for redox flow battery

Ordered Nanoporous Metals from Ionic Liquid Templates for

Structure of PEO-PEGE Block Polyethers in

Novel Multifunctional Organic Salts to Combat

A low concentration of ionic liquid dissolved in base oil

Chlorophyll extraction from spinach using aqueous solutions

Polarity control of aqueous biphasic systems using ionic

Swelling of the Near-Surface Nanostructure of

Use of ionic liquids for the separation of polyester/cotton

H-bond capacity and self-assembly of cationic surfactants in

Porous silica spheres-supported Zn-functionalized ionic

The directed formation of high-order polybromides from

Nanostructure of Ionic Liquid-Solid Interfaces Revealed with

National Cheng Kung

Electrochemical Preparation of Nanoporous poly

The effective charge of the cations and anions in EMIMFSA

Isothermal vapor-liquid equilibria for ternary mixtures of

Role of the physicochemical properties of a

Design of ion transport membranes using liquid crystalline

Prediction of effective ionic liquids extraction solvents by

University of New South

Robust and Versatile Ionic Liquids Microarray Achieved by

Sun Yat-Sen University

Solubility of Carbon Dioxide in Aqueous Solution of

King Saud University

Solubility of CO2 in Ionic Liquids Analogous: Experiments

Hydrogen Evolution at Semiconductor - Ionic Liquid

University of New South

University of New South

Novel chloroimidazolium-based ionic liquids: preparation,

Low viscosity phosphonium-based ionic liquid for

Removal of nitrogen compounds for improved efficiency of

Proton and HSCQ NMR of Cellulose and Wood in ionic

Ionic Liquids Containing Cationic Metal-Chelate Complexes

University of New South

Catalyzed Lignin Depolymerisation using Polyoxometalate

University of New South

Imidazolium-based Distillable Ionic Liquid for

High Yield Access to Imidazolium-based Fluorous Ionic