Soft Chemical Synthesis and Characterization of Nanostructured Transition Metal Oxides with Electrochemical, Electrochromic, and Photocatalytic Activities

Ah Reum Han Center for Intelligent Nano-Bio Materials (CINBM), Division of Nano Sciences and Department of Chemistry, Ewha Womans University, Seoul 120-750, Korea.

Contents
I. Soft Chemical Dehydration Route to Carbon Coating of Metal Oxide: Its Application for Spinel Lithium Manganate

II.

Soft-chemical Synthesis of Carbon-coated Titania: Effect of Carbon-Coating on the Photocatalytic Activity of TiO2
A Room Temperature Etching Route to Tungsten Oxide Hydrate Nanoplates with Expanded Surface Area

III.

IV. Hydrothermal Synthesis and Characterization of Nanocrystalline Manganese Oxide-Aluminum Oxide Nanocomposites V. A Unique Transformation from Rutile TiO2 to Anatase TiO2 Assisted by Layered Protonic Titanate

Chapter 1

Soft Chemical Dehydration Route to Carbon Coating of Metal Oxide:

Its Application for Spinel Lithium Manganate

Introduction
Advantage of Carbon Coating
on Metal Oxide
1. Enhancement of conductivity 2. Increase of absorbing ability against

Conventional Preparation Methods of Carbon Coating

1. Chemical vapor deposition 2. Pyrolysis of polymeric carbon

organic molecules
3. Protection of metal oxides from a chemical corrosion

3. Sol-gel synthesis
4. Hydrothermal decomposition of adsorbed organic precursors, etc.

Most of the methods reported contain a heattreatment step at elevated temperature or require special apparatus like a deposition machine !!!

Solution !!!
A less energy-consuming route of carbon coating is necessary !!!

Dehydration Reaction

Sucrose (C12H22O11)

H2SO4
Dehydration Reaction
C

C C

C C C

C C
C

11H2O + 6C2

Experimental
Method of Carbon-Coating
Synthesis of LiMn2O4
Li2CO3 + Mn2O3
90

Mixing and Milling

LiMn2O4 Sucrose/H2SO4 (aq)

Low temp. dehydration

Carbon-coated LiMn2O4

Pelletizing

The weight percent of sucrose with respect to LiMn2O4 was controlled to be:
1/20 (The obtained sample is donated as C1), 1/10 (The obtained sample is donated as C2),

Calcination at 650 in Air Sintering at 750 in Air

1/5 (The obtained sample is donated as C3).

Characterization Powder XRD, Raman, FE-SEM, HR-TEM, XAS, Electrochemical measurement

XRD Analysis and Lattice Parameter

Compound a () 8.2458 8.2445 8.2421 8.2328 Vc 560.658 560.393 559.904 558.011 Crystal symmetry cubic cubic cubic cubic

X-ray intensity (10 cps)

C3 2 C2
LiMn2O4 C1 C2

1 C1
(111) (311) (220) (400) (331) (511) (440)

C3

LiMn2O4 0 10 20 30

40

50

60

Two theta (degree)

All of the intense diffraction peaks could be well indexed on the basis of spinel LiMn2O4

Oxygen Manganese

Lithium

AB2O4 Spinel

Electron Microscopy
LiMn2O4 C3

1m

1m

C1

C2

C3

LiMn2O4
~10nm ~20nm

~25nm

The electron microscopic results presented clearly demonstrate that the low-temperature dehydration method is effective in forming a carbon nanolayer on the surface of metal oxide

Mn K-edge XANES Analysis

Normalized absorption coefficient
1.6
P P' C

Pre-edge peaks P & P : 1s 3d transition

1.2

6538

6541

6544

Main-edge peak A : 1s 4pp transition with a ligand-to-metal charge transfer

B
LiMn2O4 C1 C2 C3 + Mn2O3 o LiMn0.9Cr0.1O2 MnO2

0.8

0.4
P P'

Two peaks P and P are discernible commonly for the spectra of the spinel lithium manganate and its carbon coated derivatives.

0.0

6540

6550

6560

6570

Energy (eV)

Micro-Raman Analysis
G D D'
C3

Raman intensity (arb. units)

G D

Free Carbon

LiMn2O4

Langmuir, Vol. 21, No. 11, 2005 5043

1100 1200 1300 1400 1500 1600 1700 1800

Raman shift (cm )

Electrochemical Measurements
140
In comparison with the pristine LiMn2O4, the carbon coated materials show larger discharge capacity and better cyclability in the entire cycle range, underscoring the effectiveness of the present coating method in improving the electrochemical performance of electrode materials.

Discharge capacity (mAh/g)

120 100 80 60

Acid Corrosion Test

40 20 0
LiMn2O4 C1 C2

Mn (%) LiMn2O4 C1 30.00 5.00

C2
0 5 10 15

3.78
3.35

C3

Number of cycle

Conclusions
We have successfully developed a novel soft-chemical carbon coating method based on the dehydration reaction of carbohydrate molecules assisted by sulfuric acid. The carbon coated lithium manganates show better electrode performance compared to the uncoated pristine material, which would be related to the enhancement of the chemical stability of spinel lithium manganate and/or to the increase of grain connectivity.

The present method provides a novel less energy-consuming route not only to the carbon coating of metal oxides but also to the improvement of electrode performance.

J. Phys. Chem. C, 2007, 111, 11347-11352

10-2007-0068078 (2007)

Chapter 2

Soft-chemical Synthesis of Carboncoated Titania: Effect of CarbonCoating on the Photocatalytic Activity of TiO2

Research Background
What is the photocatalytst?

O2

H2O

O2-

TiO2 Photocatalyst

OH-

OxidationReduction

Organic materials

CO2+H2O

These oxidants and reductants can decompose organic materials into CO2 and H2O.

Introduction
Application and Properties of Titanium Dioxide
Photocatalysts (photodegradation of various pollutants). Photovoltaics (generation of electric power from solar energy). Electrochromic Devices (color change upon redox reaction).

Hydrogen Storage (hydrogen sorption in TiO2 nanotube).

Various Factors Affecting the Photocatalytic Activity of TiO2

Advantage of Carbon Coating on Titanium Dioxide

Crystal Structure. Crystal Morphology and Surface Area. Chemical Composition.

High Adsorptivity because of Porous Nature of Carbon Layer.

Experimental
Method of Carbon-Coating

90

TiO2
Sucrose/H2SO4 (aq) Low temp. dehydration Carbon-coated TiO2

The weight percent of sucrose with respect to TiO2 was controlled to be:

1/20 (The obtained sample is donated as C1),

1/10 (The obtained sample is donated as C2), 1/5 (The obtained sample is donated as C3).

Characterization Powder XRD, HR-TEM, Micro-Raman, XANES, Photocatalytic activity test

Powder XRD Analysis

X-ray intensity (10 cps)

C3

C2 4 C1
(101)

Regardless of the carbon coating, all the present samples show nearly the same XRD patterns, which are well indexed with anatase TiO2 structure. According to least squares fitting analysis, there is no notable variation of lattice parameters before and after the carbon coating.
(103) (004) (112) (200) (105) (211) (204) (116)

2 TiO2 0 10 20

* 30

* 50 60 70

40

Two theta (degree)

Electron Microscopy

3.3nm

14.2nm 18.2nm

The dark part in the present images represents the microcrystals of titanium dioxide while the bright part on the edge of the TiO2 crystallite corresponds to the coated carbon layer.

Ti K-edge XANES Analysis

Normalized absorption coefficient
1.5 P2 P 3 P1 1.0
This provides strong supports for the negligible influence of carbon coating on the anatase structure of titanium oxide.

4967 0.5

4972

4977 A Pristine TiO2 C1 C2 C3 Rutile 4985 4995

P1 0.0 4965

P2 P 3

4975

Energy (eV)

Micro-Raman Spectra
Raman intensity (arb.units)
40 30 C2 20 C1 10 0 300 600 900 1200 1500
-1

G C3

TiO2 1800

Raman shift (cm )

The observed peaks at 1365 and 1585 -1 can be assigned as the D and G phonon lines corresponding to the bond stretching mode of all pairs of sp2-atoms in rings and chains, and the breathing mode of bonded carbon in rings, respectively.

Degradation of Organic Dye Molecule

50
Methylene Blue (
TiO2 C1 C2 C3
1.2
293 nm

40 30 20

Absorbance

0.8

0.4

TiO2 C1 C2 C3

0.0

10
Dark Condition

10

20

Irradiation Time (hr)

0 0 30 60 90 120 150 180

Adsorptive Activity

Irradiation Time (min)

The photocatalytic activity of the carbon-coated titania was evaluated by measuring the time-dependent degradation of methylene blue (MB) in an illuminated catalyst suspension.

Conclusions
We have successfully developed a novel soft-chemical carbon coating method based on the dehydration reaction of carbohydrate molecules assisted by sulfuric acid. The carbon coated titanium dioxides show better photocatalytic activity compared to the uncoated pristine material, which would be related to enhancement of absorption ability. The present method provides a novel less energy-consuming route not only to the carbon coating of metal oxides but also to the improvement of photocatalytic performance.

J. Nanosci. & Nanotech., submitted (2007)

Chapter 3

A Room Temperature Etching Route to Tungsten Oxide Hydrate Nanoplate with Expanded Surface Area

Introduction
Applications and Properties of Tungsten Oxides
1. Optoelectronics 2. Microelectronics 3. Selective catalysis 4. Environmental engineering (Gas sensor for various gases like NOx, H2S, etc.)

Porous materials
1. High surface area 2. Influence of chemical reaction (because of adsorption)

Al137+ Etching Process WO6 WO4

We have tried to synthesize uniform sized nanoplates of crystalline tungsten oxide hydrate at room temperature through a selective etching of alumina from the adduct of tungstate and aluminum keggin cluster.

Background Research
What is electrochromic material?

Schematic description of electrochromic device

z
Some transition metal oxides, organic Polymers, and inorganic complexes show a drastic change of their absorption and reflection behaviors. This originates from the reversible oxidation/reduction of electrodes caused by the insertion/ extraction of electrical charges.
Prussian blue

z
WO3

Electrochromic Materials
1) Cathodic coloration materials WO3, TiO2, MoO3, Nb2O3, etc. 2) Anodic coloration materials NiO2, Cr2O3, MnO2, FeO2, etc.

Experimental
Synthesis Electrochromic performance
Spin Coating of Tungsten Oxide Suspension 1500rpm, 30sec, 3times

Solution of (NH4)2WO4 + Solution of Aluminum Keggin ion [AlO4Al12(OH)24(H2O)12]7+

Electrodeposition of Prussian Blue Stirring at Room Temperature

10 mM K3Fe(CN)6, 10mM FeCl3, and 10 mM HCl at aqueous solution Cathodic electrodeposition
Electrodeposition condition 1. Reference electrode - SCE (Saturated calomel electrode) 2. Counter electrode - Pt wire gauze or FTO glass 3. Working electrode - FTOGlass = ( 20 A/cm2 - 3 min.)

Separation by Centrifuging and Drying

Etching using HNO3

(selective etching of alumina)

Powder XRD Analysis

(010)

(200) (001) (020) (101) (001)

Its etched derivative

The nanocomposite consisting of Al137+ cation and WO42- anion does not show any well-developed Bragg reflections, suggestive of its X-ray amorphous nature. A chemical etching process on the composite at room temperature leads to the development of sharp diffraction peaks, which can be well indexed on the layered structure of tungsten oxide hydrate phase.
(201) (211) (220) (021)

X-ray intensity (arb. units)

As-prepared nanocomposite

15

25

35

Two theta (degree)

(221) (230) (131) (040) (022) (212)

45

55

Thermogravimetric Analysis
Etched derivative (WO3.2H2O)
a) b)

100

Weight loss (%)

The acid-etched derivative exhibits two steps of endothermic weight loss at 100 and 100-230 corresponding to the removal of weakly bounded water and the dehydroxylation of tungsten oxide, respectively.

90

1.02%

100

200

300
o

400

500

Temperature ( C)

FE-SEM Images & EDS Analysis

As-prepared nanocomposite
Its etched derivative

10m
W

100nm
BET surface area ~32m2/g

W
O Al

BET surface area

~18m2/g

O W W W W W W W W

While the nanocomposite shows irregular polyhedral morphology with large particle size of lager than several micrometers, its etched product unfolds the porous stacking structure of uniform sized nanoplates with lateral dimension of ~100 nm and the thickness of ~30 nm.

W L-edge XANES Analysis

Normalized absorption coefficient
WL
(a) - - - - - -

(b) (c) (d)

All the present compounds show an intense and broad peak around 10210 eV corresponding to the dipole-allowed transitions from 2p level to unoccupied 5d states.
As-prepared nanocomposite Its etched derivative K2WO4

0 10185

WO3

10195

10205

10215

10225

Energy (eV)

Measurements of EC property
90 80

Bleached state

Transmittance (%)

70

60

Bleached state

50

40

30

Colored state

Colored state

20 400 500 600 700 800

Wavelength (nm)
The obtained EC cell works well with the apparent change of optical density in the wavelength region of >600 nm.

Conclusion
We are successful in synthesizing crystalline tungsten oxide hydrate nanoplates at room temperature via an acidic etching process of the ion-adduct of WO42- and Al137+. The selective etching of the tungstate-aluminum keggin nanocomposite leads not only to the increase of surface area but also to the local structural change from WO4 tetrahedra to WO6 octahedra. With the obtained tungsten oxide, a full electrochromic cell can be fabricated. The present study can provide a novel less energy-consuming and more economic way of preparing crystalline tungsten oxide hydrate nanoparticles with electrochromic property.

Mater. Lett., in press (2007)

Chapter 4 Hydrothermal Synthesis and characterization of Nanocrystalline Manganese Oxide-Aluminum Oxide

Manganese Oxide
Catalytic Property
Low Temperature Synthesis High Temperature Synthesis

Irregular particle size, Poorly crystalline phase

Large particle size

It is necessary to depress the crystal growth process at elevated temperature for the purpose of synthesizing nanocrystalline manganese oxides with improved crystallinity !!!

The formation of nanocomposite composed of manganese oxide and other compound is supposed to be powerful in preventing the crystal growth of manganese oxide !!!

Experimental
Synthesis
Potassium Permanganate + Aluminum Keggin ion Solution
0.2M of Potassium permanganate + Aluminum keggin ion([Al13]+7 solution of pH 6

autoclave

Hydrothermal reaction at 70
Centrifuge at 12000rpm

Centrifuging

At 70

Washing

Powder XRD, FE-SEM, TG-DTA, BET, XAS

FE-SEM
250

N2 adsorption-desorption isotherm analysis

Amount of N2 Absorbed(mL/g)
As-prepared MnO2-Al2O3 nanocomposite Adsorption 200 Desorption

As-prepared MnO2-Al2O3

150

100nm

Its calcined derivative

100

50
BET surface area ~230m2/g

0
100nm

Relative Pressure(P/Po)

Chapter 5 A Unique Phase Transformation from Rutile TiO2 to Anatase TiO2 Assisted by Layered Protonic Titanate

Heat-treatment

Anatase

Rutile

Many attempts have been made to stabilize anatase TiO2 phase at elevated temperature !!! Doping or addition of another metal oxide to the titania or surface coating

We have been successfully transform to stabilize anatase

TiO2 phase at elevated temperature

Experimental
Synthesis of Layered H0.67Ti1.83O4
HCl-treatment Solid-state reaction Cs2CO3 + TiO2 Heat-treatmemt Sintering at 800oC in Air

1M HCl(g/100), 5 times
Ion exchange at RT

+++++ +++++

Layered Cs0.67Ti1.83O4

Layered H0.67Ti1.83O4

Method of As-prepared Ti Oxide

TiO2
(Rutile Phase)

Layered Titanate/H2O (aq)

Centrifuging and Drying

Calcinations

Powder XRD Analysis

R

Ti K-edge XANES Analysis

Normalized absorption coefficient
1.5 P2 P1 1.0 4967 0.5 P2 P1 0.0 4965
As-prepared compound Its calcined derivative Anatase TiO2 Rutile TiO2

8 7
A Its calcined derivative

P3

X-ray intensity (10 cps)

6 5 4 3 2 1 0 10 20 30 40 50 60 70
Its calcined derivative
L: Layered titanate A: Anatase As-prepared compound R: Rutile

As-prepared compound without water

4972

4977 A

P3

4975

4985

4995

Two theta (degree)

Energy (eV)

Summary

Chapter 1, 2 : Carbon Coating of Metal Oxide and its Application

Chapter 3: Porous Tungsten Oxide Hydrate Nanoplate

Chapter 4: Nanocrystalline Manganese Oxide-Aluminum Oxide Nanocomposites

Chapter 5: Transformation from Rutile TiO2 to Anatase TiO2

Thanks for your attention