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EDITORS Mohammad B. Kassim Lorna Jeffery Minggu Siti Fairus Binti Mohd Yusoff Khuzaimah Arifin
i
PROGRESS IN
PHOTOELECTROCHEMICAL RESEARCH 2014
ii
PROGRESS IN
PHOTOELECTROCHEMICAL RESEARCH 2014
Editors
Mohammad B. Kassim Lorna Jeffery Minggu
Siti Fairus Binti Mohd Yusoff Khuzaimah Arifin
FUEL CELL INSTITUTE UNIVERSITI KEBANGSAAN MALAYSIA
BANGI 2014
http://pkukmweb.ukm.my/~selfuel/
Cetakan Pertama/ First Printing, 2014
Hak cipta/ Copyright Universiti Kebangsaan Malaysia, 2014
iii
Hak cipta terpelihara. Tiada bahagian daripada terbitan ini boleh
diterbitkan semula, disimpan untuk ditukarkan ke dalam sebarang
bentuk atau dengan sebarang alat juga pun, sama ada dengan cara
elektronik, gambar serta rekaman dan sebagainya tanpa
kebenaran bertulis daripada Kumpulan Penyelidikan Hidrogen
Suria, Institut Sel Fuel, UKM terlebih dahulu.
All rights reserved. No part of this publication may be reproduced or
transmitted in any form or by any means, electronic or mechanical
including photocopy, recording or any information storage and
retrieval system, without permission in writing from Solar Hydrogen
Research Group, Fuel Cell Institute, UKM.
Diterbitkan di Malaysia oleh/ Published in Malaysia by
INSTITUT SEL FUEL
Kumpulan Penyelidikan Hidrogen Suria
43600 UKM Bangi, Selangor Darul Ehsan, Malaysia
Tel: 03-8921-6050
Fax: 03-8921-6024
http://pkukmweb.ukm.my/~selfuel/
Email: mb_kassim@ukm.edu.my
Dicetak di Malaysia / Printed in Malaysia
Progress In Photoelectrochemical Research 2014 ISBN 978-967-10935-4-2
iv
Contents
Foreword vi vi
Section I - PEC Characterisation and Testing
Photocurrent Generation with Addition of Methanol, Formaldehyde and Formic Acid
1
Ng Kim Hang, Lorna Jeffery Minggu and Mohammad B. Kassim
Enhancement of Photoelectrochemical Water Splitting Cell Photocurrent with Natural Dye from Pitaya Peel
5
Siti Nur Hidayah Jaafar, Lorna Jeffery Minggu, Mohammad B. Kassim and Wan Ramli Wan Daud
Effects of Au on Photoelectrochemical Activity of WO3 Thin Film in Electrolyte Containing Methanol
9
Nurul Akmal Jaafar, Lorna Jeffrey Minggu and Mohammad B. Kassim
Photoelectrochemical Reduction of Carbon Dioxide for Production of Fuel
13
Marinah Zainal, Lorna Jeffery Minggu, Mohammad B. Kassim, and Siti Kartom Kamaruddin
Section II - Synthesis and Pysico-Chemical Properties
N-Benzoyl-N'-(1,10-Phenanthrolin-5-Yl)Thiourea Derivatives
17
Siew San Tan and Mohammad B. Kassim
v
Synthesis and Characterization of Iridium(III) Complex with 1-benzoyl-3-(pyrid-2-yl)-1H-pyrazole Derivative
21
Chong Yan Yi, Law Kung Pui and Mohammad B. Kassim
Synthesis and Characterization of Acetonitriletricarbonyl 1-benzoyl-3-(pyridin-2-yl)-1H-pyrazole Rhenium(I) Tetrafluoroborate, {Re(BzPyPz)(CO)3CH3CN}BF4
25
Rosidah Shardin, Law Kung Pui and Mohammad B. Kassim
Synthesis and Characterization of Novel Ruthenium(II) Complexes with Benzoyl
29
Mark Lee Wun Fui, Lorna Jeffery Minggu and Mohammad B. Kassim
Preparation and Characterization of Iron(II) And Iron(III) Macrocyclic Complexes
33
Latifah M. Yusoff, Bohari M. Yamin and Siti Fairus M. Yusoff
Enhanced Thermal Stability of Liquid Natural Rubber Produced by Hydogenation Process
37
Naharullah Jamaluddin, Ibrahim Abdullah and Siti Fairus M. Yusoff
Synthesis of Cobalt Complex with 1-(1,3-benzothiazol-2-yl)-3-benzoylthiourea Ligand
41
Syahidah Binti Mohd Tahir and Mohammad B. Kassim
vi
Foreword
Solar Hydrogen group focuses on research and development to
ehnance the performance of heterogeneous photocatalyst and
photoreactor to directly split water to give hydrogen and oxygen
gas using solar energy. The research projects involve designing
and synthesizing sensitizer molecules; development of
photoelectrode; development of photoreactor incorporating the
photoelectrode for water splitting and testing of the integrated
system under simulated or real conditions.
This book consists of a collection of short papers from Solar
Hydrogen researches at the Fuel Cell Institute and Faculty of
Science and Technology, UKM. The information reported in these
papers is new and supports the master plan and the research
direction of Solar Hydrogen research group. In addition, the
research programme is also working along the direction of the
Fuel Cell and Hydrogen Technology programme for the Renewable
Energy Niche.
An appreciation goes to Dr. Siti Fairus Binti Mohd Yusoff,
Dr. Lorna Jeffery Minggu and Dr. Khuzaimah Arifin for reviewing
the manuscripts for this book.
Mohammad B. Kassim December 2014
SECTION I
PHOTOCURRENT GENERATION WITH ADDITION OF METHANOL, FORMALDEHYDE AND FORMIC ACID
Ng Kim Hang1, Lorna Jeffery Minggu1,* and Mohammad B. Kassim1,2
1 Fuel Cell Institute, Universiti Kebangsaan Malaysia. 2 School of Chemical Sciences & Food Technology, Faculty of
Science and Technology, Universiti Kabangsaan Malaysia, 43600 Bangi, Selangor, Malaysia
*lorna_jm@ukm.edu.my
INTRODUCTION
Hydrogen (H2) has the potential to be a mobile energy carrier in the future. It contains high energy density and produces only water at end use [1]. However, in the current stage, most of the H2 gas was produced from methane-steam reforming process which produces greenhouse gas (mainly carbon dioxide) [2].
In contrast, photoelectrochemical H2 production from water splitting reaction is a zero emission of greenhouse gas process. It uses naturally available solar energy and water resources. However, this process remains in low efficiency due to the limitations of the materials used as photocatalysts [3]. In these recent years, H2 production using photoelectrochemical cells to produce H2 gas from biomass-derived oxygenates was proposed [4]. This method has several advantages against the conventional H2 gas production from biomass. This PEC system can operate at a lower temperature in a smaller scale, and the separation of product gas is much easier [5]. Besides, the thermodynamic voltage requirement of oxygenate species is much smaller than the electrolysis of water [6]. These oxygenates can also improve the photocurrent generation (or hydrogen production rate) by suppressing electron-hole pair recombination at the photoelectrode [7].
Tungsten trioxide (WO3) is one of the suitable materials for photoelectrochemical water splitting reaction. It has received much attention because of its smaller band gap (2.8 eV), high stability in acidic conditions, no photo-corrosion and its valence band position is sufficiently low to oxidize water molecules [8]. It is also a mild oxidation agents that can oxidize oxygenates species.
1
The performance of WO3 in H2 production was evaluated in this paper based on the photocurrent density generated during the photoelectrochemical reactions.
RESULTS AND DISCUSSION
The photocurrent was measured in different concentration of additives under 1000 W/m2 xenon lamp irradiation with 0.5 M Na2SO4 as supporting electrolyte. All samples were purged with argon gas for 30 minutes before the photocurrent measurement.
As seen in Figure 1, the photocurrent generation was improved with the addition of methanol. The photocurrent density increased as the concentration of methanol increased. The photocurrent production was improved from 0.65 mA/cm2 to 2.0 mA/cm2 by the addition of 4 M methanol.
Fig. 1. Photocurrent density of WO3 in different concentrations of methanol.
The photocurrent generation was further improved to 2.1 mA/cm2 with an additional amount of formaldehyde (shown in Figure 2). In a PEC that contained lower concentration of additives (0.2 M and 1.0 M), the photocurrent produced by WO3 was higher in the electrolyte contained formaldehyde compared to methanol.
2
Fig. 2. Photocurrent density of WO3 in different concentrations of
formaldehyde.
Photocurrent generation with an electrolyte containing 4 M formic acid was similar to formaldehyde. However, the saturation of photocurrent shifted to a higher potential compared to a PEC containing methanol and formaldehyde electrolytes. This might be due to the pH changed after the addition of formic acid.
Fig. 3. Photocurrent density of WO3 in different concentrations of
formic acid.
3
ACKNOWLEDGEMENT
The authors would like to thank Universiti Kebangsaan Malaysia for sponsoring the project through AP-2012-009 and FRGS/1/2014/SG01/UKM/02/1.
REFERENCES
[1] Sharma D., Upadhyay S., Verma A., Satsangi V.R., Shrivastav R. & Dass S. 2014. Nanostructured Ti-Fe2O3/Cu2O heterojunction photoelectrode for efficient hydrogen production. Thin Solid Films. Doi:10.1016/j.stf.2014.12.003.
[2] Alenzi N., Liao W.S., Cremer P.S., Sanchez-Torres V., Wood T.K., Ehlig-Economides C., Cheng Z. 2010. Photoelectrochemical hydrogen production from water/methanol decomposition using Ag/TiO2 nanocomposite thin films. International Journal of Hydrogen Energy. 35:11768-11775.
[3] Choudhary S., Upadhyay S., Kumar P., Singh N., Satsangi V.R., Shrivastav R. & Dass S. 2012. Nanostructured bilayered thin films in photoelectrochemical water splitting – A review. International Journal of Hydrogen Energy. 37: 18713-18730.
[4] Ni M., Leung D.Y.C., Leung M.K.H. & Sumathy K. 2006. An overview of hydrogen production from biomass. Fuel Process Technology. 87: 461-472.
[5] Esposito D.V., Chen J.G., Birkmire R.W., Chang Y. & Gaillard N. 2011. Hydrogen production from photo-driven electrolysis of biomass-derived oxygenates: A case study on methanol using Pt-modified WO3 thin film electrodes. International Journal of Hydrogen Energy. 36: 9632-9644.
[6] Sasikumar G., Muthumeenal A., Pethaiah S.S., Nachiappan N. & Balaji R. 2008. Aqueous methanol electrolysis using proton conduction membrane for hydrogen production. International Journal of Hydrogen Energy. 2008. 33: 5905-10.
[7] Lianos P. 2011. Production of electricity and hydrogen by photocatalytic degradation of organic wastes in a photoelectrochemical cell, the concept of the photofuelcell: A review of a re-emerging research field. Journal of Hazardous Materials. 185:575-590.
[8] Ng K.H., Minggu L.J. & Kassim M.B. 2013. Gallium-doped tungsten trioxide thin film photoelectrodes for photoelectrochemical water splitting. International Journal of Hydrogen Energy. 38: 9585-9591.
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