Oxygen network formation for efficient charge transport and durable BiVO4 photoanodes with ultra-thin TiO2 layer in solar water splitting

Bismuth vanadate (BiVO4) has emerged as a prominent oxide semiconductor in solar water splitting investigations owing to facile synthesis and favorable band-alignment with the water oxidation level. Oxygen and oxygen vacancies (VO) within the BiVO4 exhibit multifaceted roles across bulk, surface, an...

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Bibliographic Details
Main Authors: Kun Woong Lee, Dong Su Kim, Su Yeon Jung, Joohoon Kang, Hyung Koun Cho
Format: Article
Language:English
Published: Elsevier 2025-06-01
Series:Applied Surface Science Advances
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Online Access:http://www.sciencedirect.com/science/article/pii/S2666523925000455
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Summary:Bismuth vanadate (BiVO4) has emerged as a prominent oxide semiconductor in solar water splitting investigations owing to facile synthesis and favorable band-alignment with the water oxidation level. Oxygen and oxygen vacancies (VO) within the BiVO4 exhibit multifaceted roles across bulk, surface, and interface. This study presents a method for selectively regulating the surface and bulk VO in BiVO4 through facile chemical redox reactions. A large amount of VO on the BiVO4 surface enables the formation of a robust networking interface with oxide-based protection overlayers, whereas VO in bulk region must be effectively suppressed. A significant amount of VO can be specifically formed on the BiVO4 surface via a controlled surface chemical reduction reaction (SCR) at the atomic level, precisely controlling the presence of O2- and OH- ions. Here, we quantitatively and qualitatively analyze VO changes and the impact of VO on photoelectrochemical operation. As a result, The SCR process allows for the strategic control of the BiVO4 surface into a VO-rich surface. The controlled surface enhances the charge kinetic by promoting the conformal coating of a n-TiO2 protective layer and decreasing the charge loss in the interface junction with ensuring stability. Furthermore, the SCR-BiVO4/TiO2/CoPi photoanodes exhibit a highly stable photocurrent density of 3.9 mA cm−2 at 1.23 VRHE. Surface modification and understanding of the oxygen-end network can be broadly applied to photoelectrodes that require oxide-based overlays.
ISSN:2666-5239