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Comparison of Inexpensive Photoanode Materials for Hydrogen Production Using Solar Energy. N.Cook, R. Gallen S. Dennison , K. Hellgardt, G.H. Kelsall, Department of Chemical Engineering Imperial College London, SW7 2AZ, UK s.dennison@imperial.ac.uk. 216 th ECS Meeting: October 8, 2009.
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Comparison of Inexpensive Photoanode Materials for Hydrogen Production Using Solar Energy N.Cook, R. Gallen S. Dennison, K. Hellgardt, G.H. Kelsall, Department of Chemical EngineeringImperial College London, SW7 2AZ, UK s.dennison@imperial.ac.uk 216th ECS Meeting: October 8, 2009
H2 as sustainable energy carrier? 2 adapted and modified from J.A.Turner, Science 285, 687(1999)
Plugging the energy gap (14TW) Combined area of black dots would provide total world energy demand 3
Solar Hydrogen at Imperial • £4.2M EPSRC sponsored project (5 years) • Chemical Engineering, Chemistry, Biology, Earth Science and Engineering • Approx. 20-25 researchers at any one time • 2 strands: Biophotolysis and Photoelectrochemistry • Chemical Engineering to develop devices and reactors and technology for scale-up and scale out 4
Application • Targets: • Biophotolytic H2: £5.00/kg; • Photoelectrolytic H2: £2.50/kg • Fuel Cell Operation • Distributed Market 5
Candidate Materials • TiO2: Eg ~ 3.0-3.2 eV (410-385 nm) • Fe2O3: Eg ~ 2.2 eV (>565 nm) • WO3: Eg ~ 2.6 eV (475 nm) 6
Photoelectrolysis – Materials Evaluation • Photocurrent Spectroscopy • Photo-electrochemical activity of photo-anodes based on transition metal oxides (Fe, W, Ti) • Fe-based system needs bias but otherwise promising (& cheap) 10
WO3: further investigations • From H2WO4: • Electrodeposition: potential cycling -0.4 - +0.8 V vs. SCE 1 • “Doctor blading”: using stabilised H2WO4 sol 2 • Both annealed: 15 min at 550°C 1 Santato et al., J Amer Chem Soc, 2001, 123, 10639 2 Kulesza and Faulkner, J Electroanal Chem, 1988, 248, 305 11
Ir/IrO2 Electrodeposition • Ir: • From “IrCl3,aq” : E0 = +0.86 V vs NHE 1 • Convert to IrO2 by electrochemical oxidation 2 • IrO2: • From [IrCl6]3-/oxalate @ pH 10.5/galvanostatic deposition 3 1 Munoz and Lewerenz, J Electrochem Soc, 2009, 156, D184 2 Elzanowska et al. Electrochim Acta, 2008, 53, 2706 3 Marzouk, Anal Chem, 2003, 75, 1258 13
Ir Electrodeposition – Cycle 1 Vitreous carbon electrode: 10 mM IrCl3/0.5 M KCl Sweep rate: 0.01 Vs-1 Ir nucleation 14
Ir Electrodeposition – Selected Cycles Vitreous Carbon electrode 10 mM IrCl3/0.5 M KCl Sweep rate: 0.01 Vs-1 15
IrO2 Electrodeposition H2IrCl6 + (COOH)2 (pH 10.5, K2CO3) Sweep rate: 0.01Vs-1 16
Effect of IrO2 on WO3 Photoresponse 1M H2SO4 Sweep rate: 0.01 Vs-1 17
Mott-Schottky analysis following IrO2-coating 1M H2SO4 Modulation frequency: 10 kHz 18
Conclusions • The electrodeposition of Ir and IrO2 is interesting! • Deposition of Ir & IrO2 onto WO3 results in loss of photoelectrochemical O2 evolution activity. • This is due to: a) deposition of excessive quantities of Ir/IrO2 b) irreversible damage of the WO3 (MS data). 19
Design and Development of a Photoelectrochemical Reactor • Key criteria: • Optimising illumination of photoelectrode • Optimising fluid and current distributions • Product separation • Minimising bubble formation • Materials (of construction) selection 20
Photoelectrolytic Reactor: conclusions • Main contributing factors to response: • Photoanode material quality • Cathode gauze too coarse • Large illumination losses (mirror, etc.) 27
Future Work • Materials fabrication: WO3 and Fe2O3 • Photoelectrochemical reactor: • Photoanode material quality • Reduce shading by cathode • Hydrogen measurement and collection • Fully develop reactor model 28