Chemisorption of Anionic Species from the Electrolyte Alters the Surface Electronic Structure and Composition of Photocharged BiVO4

Nienke J. Sfiret, Anirudh Venugopal, Marijn A. Blommaert, Chiara Cavallari, Christoph J. Sahle, Alessandro Longo*, Wilson A. Smith

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

22 Citations (Scopus)
67 Downloads (Pure)


Photocharging has recently been demonstrated as a powerful method to improve the photoelectrochemical water splitting performance of different metal oxide photoanodes, including BiVO4. In this work, we use ambient-pressure X-ray Raman scattering (XRS) spectroscopy to study the surface electronic structure of photocharged BiVO4. The O K edge spectrum was simulated using the finite difference method near-edge structure program package, which revealed a change in electron confinement and occupancy in the conduction band. These insights, combined with ultraviolet-visible spectroscopy and X-ray photoelectron spectroscopy analyses, reveal that a surface layer formed during photocharging creates a heterojunction with BiVO4, leading to favorable band bending and strongly reduced surface recombination. The XRS images presented in this work exhibit good agreement with soft X-ray absorption near-edge structure spectra from the literature, demonstrating that XRS is a powerful tool to study the electronic and structural properties of light elements in semiconductors. Our findings provide direct evidence of the electronic modification of a metal oxide photoanode surface as a result of the adsorption of electrolyte anionic species under operating conditions. This work highlights that the surface adsorption of these electrolyte anionic species is likely present in most studies on metal oxide photoanodes and has serious implications for the photoelectrochemical performance analysis and fundamental understanding of these materials.

Original languageEnglish
Pages (from-to)7453-7462
Number of pages10
JournalChemistry of Materials
Issue number18
Publication statusPublished - 2019


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