Proceedings of September Meeting 2016 (NFM16)
Publication date: 14th June 2016
Photoelectrochemical (PEC) water oxidation on metal oxide semiconductors is central to many approaches for solar-driven fuel synthesises. Bismuth vanadate (BiVO4) is a particular promising photoanode material for water oxidation. The photocurrent and onset potential for water oxidation have reported > 4 mA cm-2 at 1.23 V vs RHE and ~0.2 V vs RHE, respectively. However, these results were obtained from a small sized photoelectrode (~ 1 cm2), in which limiting factors such as substrate conductivity, electrolyte pH gradient and mass transport were not considered. In addition, the onset potential of water oxidation on BiVO4 is limited around 0.2 V vs RHE due to the positive valence band edge (0.1 V vs RHE). Negatively shifting the valence band edge of BiVO4 can in principle reduce the anodic potential required for driving PEC water oxidation. Surface modification with electrocatalyst (such as CoPi) has shown its effectiveness in enhancing photocurrent density and reducing onset potential. However, many reports have indicated that CoPi does not catalyse water oxidation on BiVO4 surface, rather retard surface recombination. Such striking results emphasise the importance in improving charge transfer between BiVO4 and CoPi to realise the catalytic reaction to be more favourable.
In my poster, I will present PEC results of BiVO4 photoanodes with 50 cm2 active area. Particularly I will address the impact of these limiting factors upon PEC performances, and present a bias-free PEC water splitting device coupling with silicon solar cells. In addition, I will present preliminary results of using dipole molecules to surface modify BiVO4 photoanodes for more favourable onset potential and higher photocurrent. Results of a series of characterisations will be presented to demonstrate the band edge shift with surface modification using dipole molecules. Finally, I will present the attempts from our group for improvement of the charge transfer kinetics between BiVO4 and CoPi to facilitate catalytic water oxidation on the CoPi side.
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