PSM Research Proposal

Title
Student name
Matrix no.
Program:

Photocatalysis of glycerol solution

Ang Chun How
KA10132
BKC

Executive summary
The demand of biodiesel in world brought a high production biodiesel. At the same time,
glycerol as by-product is generating at about 10% of the feedstock. In Malaysia, glycerol is
classified as waste and the surplus of glycerol in the market has created a dramatic decrease
in glycerol prices. Hence, it is a need to convert of low-priced glycerol into higher value
products. Hydrogen is considered as a non-polluting fuel because when it undergoes
combustion, water is the only product generated. However, about 95% of hydrogen consumed
in the world still produced from fossil fuels mainly by catalytic thermal and gasification
processes at high temperature. Several papers have addressed the production of hydrogen
from glycerol solution using catalyst. Thus, photocatalysis of glycerol solution is believed to
solve the problems. In this study, titanium dioxide is acted as the catalyst which copper
dopant on it which different loading. The doping of copper on titanium dioxide is to extend
the optical response of titanium dioxide. The photocatalyst is prepared using wet
impregnation method. Comparisons of the performance of these catalysts will be carried out
to determine the most suitable composition for glycerol photo-reforming. The catalyst with
15% of Cu content is expected to be the best performed catalyst for glycerol photo-reforming.
Key words: Glycerol solution,

Photocatalysis, Photo-reforming, Cu/TiO2

1.0

MOTIVATION, PROBLEM STATEMENT AND BRIEF REVIEW

The current global economy is largely dependent on fossil fuels, from heavy industries to
transportation as well as daily producesFor centuries, mankind has been depending on fossil
fuel for life sustainability. The indiscriminatorye burning of fossil fuels however nevertheless
has led to environmental degradationdegraded the environment. Moreover, these fossil
hydrocarbon sources are not renewable. Hence, an alternative in the form of renewable
energyfuel such as hydrogen (H2) is fast gaining attention from the researchers (Yoong et al.,
2009). According to Das and Veziroglu (2001), H2hydrogen is the most plentiful element in
the universeal, representing an approximately three-quarters of all the matters. Significantly,
during the H2hydrogen combustion, water is the only compound being generated. Therefore,
compared to other fuels as per se, H2hydrogen is perceived as a non-polluting fuel and
scientifically has been proven harmless to human and environment.
In the year 2011 alone, National Biodiesel Board (NBB) has reported a production of more
than 802 million gallons of biodiesel, far superseding 2010 production of just( 315 million
gallons). Biodiesel, or also known as the mono-alkyl esters of long chain fatty acid, is derived
from the transesterification reaction between vegetable oils or animal fats with alcohol in the
presence of or without a catalyst (Atanani et al., 2012). According to Leoneti et al. (2012),
biodiesel production generates glycerol as by-product. Abad and Turon (2012) estimate this
generation at about 10% of the feedstock. Nonetheless, the burgeoning diesel industry
creates a glut of glycerol due to the lack of downstream consumptions; hence a potential
industrial waste (Slamet et al., 2011).
The continuous production of biodiesel as future liquid transportation fuel is anticipated to
increase; hence the glycerol production. In Malaysia, glycerol is classifieds as waste under
Schedule S181 of the Environmental Regulations in Malaysia and stored in drums and
disposed off in landfills (Hidawati & Sakinah, 2011). Currently in Malaysia, Kualiti Alam
Waste Management Centre is the only body handling these scheduled wastes where disposal
and its treatment are carried out at prescribed premises only with a certain amount of charges
imposed for every tone of waste disposal. The cost for landfill is ~RM 500 and incineration
~RM 810-RM 3600t-1 (Hazimah et al., 2003).
Moreover, the amount of glycerol generated has increased tremendously because the
biodiesel market is being expanded around the world, this lead to the problem the
surplus of glycerol in the market (Sreethawong et al., 2011). According to Varrone et al.
(2012), the considerable growth of the biodiesel industry has created a dramatic decrease in
crude glycerol prices., Significantly, this decrease in prices fallout poses a problem for the
glycerol-producing and refining industries, and consequently the economic viability of the
biodiesel industry itself has been greatly affected. Therefore, the development of processes to
convert low-priced glycerol into higher value products is expected required to boost the
income of to the development of biorefineries and also adds value to the production of
biodiesel (Dharmadi et al., 2006).
However, so far about 95% of hydrogen consumed in the world still produced from fossil
fuels mainly by catalytic thermal and gasification processes at high temperature (Slamet et
al., 2011). Numerous methods have been proposed to produce hydrogen from renewable
sources, however, sustainable hydrogen production from solar photocatalytic splitting of
water is the ultimately challenging dream (Gombac et al., 2011).
These Significantly, for the past few years, the researchers studies on crude glycerol
utilization have begun to focused on its conversion into valuable product. In fact, several
papers have addressed the production of hydrogen from glycerol solution using catalyst (Skaf

et al., 2012). According to a review by Melo and Silva (2011) have provided an excellent
review of , different methods to producefor hydrogen production from glycerol, viz. had been
tested in the past such as steam reforming, gasification, autothermal reforming, aqueousphase reforming, electrochemical reforming, photofermentation and supercritical water
reforming processes. All these studies however have ffocused oin thermochemical routes.
Alternative to these, hydrogen can be produced from biomass in ambient conditions
(temperature and pressure) via a photocatalytic route which offers an efficient, ecologically
benign and low-cost process based on photochemical cells operating with two redox system.
1.1

OBJECTIVE

This research is aimed to synthesis and to study the physicochemical properties of titania
supported copper Cu/TiO2 photocatalyst for photo-treatment of glycerol solution.
1.2

SCOPE

In order to achieve the objectives of the current work, the following scopes have been
identified:

I.

II.

a) To synthesize Cu/TiO2 photocatalyst using wet impregenationimpregnation

method with the dopant metal loadings ranging from 2 to 25 wt%. of :
b) 2 wt%
c) 5 wt%
d) 10 wt%
e) 15 wt%
f) 20 wt%
g) 25 wt%
To characterize the physicochemical properties of Cu/TiO 2 photocatalyst using
spectroscopic analyses such as:
a) X-ray Photoelectron Spectroscopy (XPS)
b) Liquid Nitrogen Physisorption
c) UV-Vis
d) Field Emission Scanning Electron Microscopy (FESEM)
e) X-ray Diffraction (XRD)
f) Scanning Electron Microscopy (SEM)
To study the effect of different metal loadings of Cu/TiO2 photocatalyst on the photoreforming of glycerol solution.

2.0

LITERATURE REVIEW

2.1

PHOTOCATALYTIC OF GLYCEROL

According to Carp et al. (2004), photocatalytic process can described as the semiconductor
can be excited light-induced excitation. by light The light supplies with higher energy than
the material band gap and an energy-rich electron-hole pair is formed as illustrated in
Fig.2.1.1. The mechanism of photocatalysis is thatinvolves photoabsorption of a
semiconducting material occurs tothat excites electron from the valence band to the

conduction band leaving positive valence band. This creates, an electron (e-)-hole (h+) pair
(e - h+) is generate (Othani, 2011).

Fig. 2.1.1. Photo-absorption by a semiconductor causesby electron transitions of electrons

infrom the valence band to the conduction band in a semiconductor.
According to Melo and Silva (2011), in theall case of photocatalytic reforming of glycerol,
there are hydrogen and carbon dioxide were produced. The general reforming of glycerol
follow this stoichiometry equation below:This process when applied to any oxygenated
hydrocarbons can be represented by Eqn. (1).
CxHyOz + (2x-z) H2O xCO2 + (2x-z+y/2) H2

(1)

The For glycerol photo-reforming, the primary reaction can be shown as in Eqn. (2) of
glycerol having general equation as below:.
C3H8O3 + 3H20O 3CO2 + 7H2

(2)

According to Panagioto et al. (2012), ) mentioned that a photo-reforming reaction typically

takes place under unaerated conditions., tTherefore, photogenerated holes are utilized to
oxidize the organic compound (Fig. 2.1.2. (b)) and the electron and electron are free to reduce
water towards hydrogen (Fig. 2.1.2. (a)). Significantly, Tthe rate of hydrogen generation
under photo-reforming is much morecomparatively higher compared tothan photocatalytic by
water photo-splitting of water becauseattributed to the efficient scavenging of the
photogenerated holes are scavenged efficiently by the organic substrate.
(a)

(b)
Fig. 2.1.2. Simplified mechanistic scheme showing the reaction occur over Cu/TiO2
suspensions under glycerol photo-reforming.

2.2

GLYCEROL

According to Dasari et al. (2005), for every 9 kg of biodiesel produced, about 1 kg of a

glycerol by-product is formed. The usage of low-grade quality of glycerol is a big challenge
because glycerol cannot direct used for food and cosmetic usesHence, the effective usage or
conversion of glycerol will cut down the biodiesel production costs (Pachauri & He, 2006).
Glycerol (also known as 1,2,3-propanaetriol, glycerine, glycerin, glycyl alcohol) id s a
trihydric alcohol. It is a colourless, odorless, and sweet-tasting, syrupy liquid. Glycerols
molecular weight is 92.09382., It melts at 17.8C and boils with decomposition at 290C.
Glycerol is completely soluble in water and alcohol,; slightly soluble in ether, ethyl acetate
and dioxane; and insoluble in hydrocarbons. The chemical formula for glycerol is:
OH CH2 CH(OH) CH2 OH

2.3

TITANIUM DIOXIDE, TiO2 AS PHOTOCATALYST

Titanium is the worlds fourth most abundant metal after aluminium, iron and magnesium, it
was discovered by Reverend William Gregor in 1791 in England (Carp et al., 2004). Titanium
dioxide or titania (TiO2) is the transition metal oxides. In 1972, Honda and Fujishima first
observed the effect of photosensitization of electrode on the water electrolysis into hydrogen
and oxygen. As a photocatalyst, TiO2 is always employed used in the catalytic reactions, it
acted either as a promoter, or a carrier for metal or metal oxides, an additive or as a catalyst.
According to Yoong et al. (2009), TiO 2 is considered as a good photocatalyst for hydrogen
generation because of itsit possesses excellent resistancet to chemical and photochemical
corrosion in aggressive aqueous environments., besides Besides that, it is also performs high
activities towards light and water.
As showed in Fig. 2.3., TiO2 consists of the valance band and conduction band; most
electrons are located in the valence band at ambient temperature. Once the TiO 2 is is
illuminated with photon which with wavelength greater than 280 nm, the electrons, e - in the
valence band will be excited to conduction band and lleaving behind the positive holes h+ in
the valance band. If the e- and h+ on the surface meet the electron acceptors or donors, they
will participate in the redox reaction, this the mechanism of TiO2 acted as photocatalyst
(Hongfei, 2005).

Fig. 2.3. Redox reaction occurring in and on TiO2 during photocatalytic mineralization of
organic molecules by oxygen.

However, TiO2 only can absorb the ultraviolet light of the solar energy due to its large band
gap of 3.0 eV (Tang et al., 2012);, this limits the research that undergoingassociated with
visible light range (400 750 nm). Hence, many efforts have been made to extend the optical
response of TiO2 including doping of nonmetal or transition metal. Table 2.3 showsed some
of the example ofprevious works related to the metal doping to TiO2 of pass research.
Table 2.3 Examples of doping on TiO2.
Activator
Visible light
Visible light
Visible light
Visible light
Visible light

3.0

METHODOLOGY

3.1

CHEMICAL

Doping on TiO2
Nitrogen
Copper
Copper oxide
Copper and Platinum
Platinum

References
Slamet et al., 2011
Yoong et al., 2009
Gombac et al., 2009
Skaf et al., 2012
Panagiotopouou et al., 2012

The tTable 2.1 showsed the chemicals involved in the catalyst preparation, photocatalytic
reaction and photocatalyst characterization analysis.
Table 3.1 Lists of chemicals
Chemical
Degussa P25 TiO2
Cu(NO3)2.3H2Oo
Glycerol solution
Potassium bromide KBr
(FTIR grade)
N2/He mixture
He
N2
NH3/N2 mixture
3.2

Purity
Application
80% anatase, 20% rutile, Catalyst preparation
BET surface area
>98%
Catalyst preparation
95%
Photocatalytic reactant
99%
FTIR analysis
N2=30.03%, He=balance
> 99.996%
> 99.99%
NH3=10.04%, N2=balance

BET analysis
BET analysis
BET analysis
FTIR analysis

CATALYST PREPARATION

In this research study, Cu/TiO2 will be the photocatalyst. According to Tang et al. (2012),
doping of nonmetal or transition metal onto TiO2 will increase the activity of photocatalytic.
In this research, the catalyst preparation will be following Yoong et al. (2009)s research
which is wet impregnation. Wet impregnation is a widely used catalyst preparation technique
where the precursor material is dissolved in a solvent and mixed with the solid support.
Degussa P25-TiO2 photocatalyst containing predominantly anatase phase and having a
specific surface area of 50 m2/g will be sourced from Sigma-Aldrich. The metal dopant
precursor, copper nitrate trihydrate, Cu(NO3)2.3H2O (Acros, >98% purity),will be diluted
with distilled water to the purity of 2% in a beaker. The accurately-weighed TiO 2 will be

added to the 2% copper nitrate solution prepared and the resulting slurry is to be stirred for 1
h by magnetic stirrer. Subsequently, it will be evaporated by water-bath the beaker containing
the slurry at 80 oC to allow the precursor deposition onto the base material. Finally, the solid
material will be oven-dried at 120oC for overnight followed by air-calcined at 300oC for 30
minutes. Preparation of other metal loadings, viz. 5%, 10%, 15%, 20% and 25% of copper
metal will follow the same outlined procedures.
**Temporary used this, will derived later on

3.3
PHOTOCATALYST CHARACTERIZATION
The catalyst prepared was will be characterized by the methods mentioned in Section 1.2.
The detailsmethods listed in Table 3.3.
Table 3.3 The lists of catalyst characterization techniques and its equipment.
Techniques
Equipment
XPS
JPS-9010
BET
Autosorb-1 , AS1 WIN
UV-Vis
Jasco V-550 Spectrophotometer
FESEM
JEOL JSM-7800F
XRD
Philips X Pert System
SEM
Hitachi S900 SEM
3.4

PROCEDURE OFGLYCEROL PHOTO-REFORMING

Reactions are performed at atmospheric pressure and 40C using a 500 mL three port Pyrex
round bottom flask containing 250 mL of glycerol solution combined with 585 mg of
catalyst. For certain runs, EnviroGem AD01 surfactant (Air Products) or Surfynol MD-20
defoamer (Air Products) is added to reduce foaming. The mixture is sonicated for 45 min in
the reaction flask to disperse the catalyst. Argon is bubbled through the solution for
approximately 4 hour prior to the reaction to deoxygenate the system. Photoreactions are
performed using UVA-340 lamps (Q-Lab) and a radiometer is used to measure an incident
light intensity of 5.1 9 10-5 Einstein/m2 s. Argon flow is continued during the reaction and a
sampling valve delivered 500 uL of gas to a 5890 GC equipped with a Shin Carbon RT
column and TCD detector. Gas samples are analyzed every 15 minutes for the first 4 hour of
reaction and every 30 minutes thereafter.

4.0

RESEARCH PLAN

4.1

CHEMICALS AND CONSUMABLES PROCUREMENT

The chemicals need for this research is listed in Table 3.1. During week 3, research
supervisor, Dr. Cheng Chin Kui had a meeting with student to discuss about the chemicals
needed then a requisition form had filled and approved by Dr. Cheng on week 4. On the same
week, the requisition form was submmited to the technical unit of Universiti Malaysia
Pahang (UMP) to purchase the chemicals. The Degusa P25 TiO 2, Cu(NO3)2.3H2O and
glycerol solution will be obtained from Sigma-Aldrich; the KBr, N 2/He mixture, He, N2 and
NH3/N2 mixture use for spectroscopic analyses will also obtain from Sigma-Aldrich.

4.2

GANTT CHART

The gannt chart stated the activities of research study along the 14 weeks, semester II
2012/2013. The details were listed in the gannt chart below.

GANNT CHART
ACTIVITIES
Title approval and
submission
Journal review
Chemical purchasing
Meeting with Supervisor
Proposal writing
Presentation form
submission
Proposal submission
Proposal presentation
Thesis writing
Photocatalyst preparation
Thesis revision
Thesis submission
4.3

WEEK
8 9
10

11

12

13

SUMMARY

Photo-reforming ofn glycerol is believe will overcome the problem ofoffers a promising
solution to the overwhelmed of glycerol supply glutin the market and add the value of
glycerol. At the same time, it can produce a clean fuel, hydrogen which can reduce the
environmental problem. Cu/TiO2 photocatalyst is believed can increase the generation of
hydrogen during photo-reforming of glycerol. Hence, photo-reforming of glycerol should be
continue study and develop it to a mature and stable technique.

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Alexandre. B.L., Valquiria. A.-L., & Sonia. V.W.B.O (2012). Glycerol as a by-product of
biodiesel production in Brazil: Alternatives for the use of unrefined glycerol.
Renewable Energy(45), 138-145

14

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Carp. O., Huisman. C.L., & Reller. A. (2004). Photoinduced reactivity of titanium dioxide.
Progress in Solid State Chemistry(32), 33-177.
Das. D., &. Veziroglu. T.N. (2001). Hydrogen production by biological processes: a survey
of literature. International Journal of Hydrogen Energy(26), 13-28.
Dasari. M.A., Kiatsimkul. P., Sutterlin. W.R., & Suppes. G.J. (2005). Low-pressure
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225-231.
Fujishima. A., & Honda. K. (1972). Electrochemical photolysis of water at a semiconductor
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