Using Transient Spectroscopic Techniques to Investigate the Effect of Catalyst Overlayers and Morphology on the Water Oxidation Performance of Bismuth Vanadate
Shababa Selim a, Laia Francas a, Camilo Mesa a, Sacha Corby a, Dongho Lee b, Andreas Kafizas a, Kyoung-Shin Choi b, James Durrant a
a Department of Chemistry, Imperial College London, South Kensington Campus London, London, United Kingdom
b Department of Chemistry, University of Wisconsin–Madison, Madison, WI 53706, USA
Materials for Sustainable Development Conference (MATSUS)
Proceedings of nanoGe Fall Meeting19 (NFM19)
#SolFuel19. Solar Fuel Synthesis: From Bio-inspired Catalysis to Devices
Berlin, Germany, 2019 November 3rd - 8th
Organizers: Roel van de Krol and Erwin Reisner
Oral, Shababa Selim, presentation 086
DOI: https://doi.org/10.29363/nanoge.nfm.2019.086
Publication date: 18th July 2019

The photoelectrocatalytic performance (i.e. water oxidation) of semiconducting materials as photoanodes is continually optimised through the implementation of nanostructuring and catalyst overlayers. Yet, the exact origin of this photoelectrocatalytic enhancement can often remain elusive. In this work we present direct spectroscopic evidence that the enhanced performance of FeOOHNiOOH coated BiVO4 results from irreversible hole transfer to the catalyst layer and consecutive hole transfer to the electrolyte to oxidise water. This hole transfer spatially separates the photogenerated charge, thus slowing down recombination. Moreover, despite not directly enhancing the kinetics of the catalytic process, we have demonstrated using steady state spectroscopic measurements that holes accumulated on the catalyst layer are responsible for oxygen generation. Additionally, charge tranport is a crucial factor that needs to be considered when optimsing electrodes for catalysis. Our thermal studies shed light on the importance of oxygen vacancies on electron transport processes that govern the overall photoelectrocatalytic performance of metal-oxide based photoanodes for water oxidation.

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