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Interface engineering for light-driven water oxidation: unravelling the passivating and catalytic mechanism in BiVO₄ overlayers

Liu, Guiji and Eichhorn, Johanna and Jiang, Chang-Ming and Scott, Mary C. and Hess, Lucas H. and Gregoire, John M. and Haber, Joel A. and Sharp, Ian D. and Toma, Francesca M. (2019) Interface engineering for light-driven water oxidation: unravelling the passivating and catalytic mechanism in BiVO₄ overlayers. Sustainable Energy and Fuels, 3 (1). pp. 127-135. ISSN 2398-4902. doi:10.1039/C8SE00473K.

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Artificial photosynthetic approaches require the combination of light absorbers interfaced with overlayers that enhance charge transport and collection to perform catalytic reactions. Despite numerous efforts that have coupled various catalysts to light absorbing semiconductors, the optimization of semiconductor/catalyst as well as catalyst/electrolyte interfaces and the identification of the role of the catalyst still remain a key challenge. Herein, we assemble (NiFeCoCe)Oₓ multi-component overlayers, interfaced with bismuth vanadate photoanodes, and determine the roles of different elements on promoting interfacial charge transfer and catalytic reaction over competitive photocarrier recombination loss processes. Through this understanding, and aided by complementary macroscopic photoelectrochemical measurements and nanoscale atomic force microscopy techniques, a bifunctional (CoFeCe/NiFe)Oₓ overlayer was rationally engineered. The resulting multi-functional coating yields BiVO₄ photoanodes with almost 100% efficient surface collection of holes under oxygen evolving reaction conditions. The (CoFeCe)Oₓ component excels at efficient capture and transport of photogenerated holes in BiVO₄ through the availability of redox active states, whereas (NiFe)Oₓ plays a vital role in reducing charge recombination at the BiVO₄/electrolyte interface. In addition, this study supports the hypothesis that catalytic sites act as electronically active trap states on uncoated BiVO₄ photoanodes.

Item Type:Article
Related URLs:
URLURL TypeDescription Information
Liu, Guiji0000-0002-3943-4119
Eichhorn, Johanna0000-0003-2413-6079
Jiang, Chang-Ming0000-0001-8327-5760
Gregoire, John M.0000-0002-2863-5265
Haber, Joel A.0000-0001-7847-5506
Sharp, Ian D.0000-0001-5238-7487
Toma, Francesca M.0000-0003-2332-0798
Additional Information:© 2018 The Royal Society of Chemistry. The article was received on 26 Sep 2018, accepted on 12 Oct 2018 and first published on 12 Oct 2018. This study is based on work performed at the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award Number DE-SC0004993. Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. There are no conflicts to declare.
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
Department of Energy (DOE)DE-AC02-05CH11231
Issue or Number:1
Record Number:CaltechAUTHORS:20181116-091613557
Persistent URL:
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:90953
Deposited By: Tony Diaz
Deposited On:16 Nov 2018 18:23
Last Modified:26 Apr 2022 17:25

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