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Combinatorial Alloying Improves Bismuth Vanadate Photoanodes via Reduced Monoclinic Distortion

Newhouse, P. F. and Guevarra, D. and Umehara, M. and Reyes-Lillo, S. E. and Zhou, L. and Boyd, D. A. and Suram, S. K. and Cooper, J. K. and Haber, J. A. and Neaton, J. B. and Gregoire, J. M. (2018) Combinatorial Alloying Improves Bismuth Vanadate Photoanodes via Reduced Monoclinic Distortion. Energy and Environmental Science, 11 (9). pp. 2444-2457. ISSN 1754-5692.

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Improving the efficiency of solar-powered oxygen evolution is both critical for development of solar fuels technologies and challenging due to the broad set of properties required of a solar fuels photoanode. Bismuth vanadate, in particular the monoclinic clinobisvanite phase, has received substantial attention and has exhibited the highest radiative efficiency among metal oxides with a band gap in the visible range. Efforts to further improve its photoelectrochemical performance have included alloying one or more metals onto the Bi and/or V sites, with progress on this frontier stymied by the difficulty in computational modelling of substitutional alloys and the high dimensionality of co-alloying composition spaces. Since substitutional alloying concurrently changes multiple materials properties, understanding the underlying cause for performance improvements is also challenging, motivating our application of combinatorial materials science techniques to map photoelectrochemical performance of 948 unique bismuth vanadate alloy compositions comprising 0 to 8% alloys of P, Ca, Mo, Eu, Gd, and W along with a variety of compositions from each pairwise combination of these elements. Upon identification of substantial improvements in the (Mo,Gd) co-alloying space, structural mapping was performed to reveal a remarkable correlation between performance enhancement and a lowered monoclinic distortion. First-principles density functional theory calculations indicate that the improvements are due to a lowered hole effective mass and hole polaron formation energy, and collectively, our results identify the monoclinic distortion as a critical parameter in the optimization and understanding of bismuth vanadate-based photoanodes.

Item Type:Article
Related URLs:
URLURL TypeDescription Information Paper
Newhouse, P. F.0000-0003-2032-3010
Guevarra, D.0000-0002-9592-3195
Umehara, M.0000-0001-8665-0028
Reyes-Lillo, S. E.0000-0003-0012-9958
Zhou, L.0000-0002-7052-266X
Suram, S. K.0000-0001-8170-2685
Cooper, J. K.0000-0002-7953-4229
Haber, J. A.0000-0001-7847-5506
Neaton, J. B.0000-0001-7585-6135
Gregoire, J. M.0000-0002-2863-5265
Additional Information:© 2018 The Royal Society of Chemistry. The article was received on 18 Jan 2018, accepted on 06 Jun 2018 and first published on 09 Jun 2018. This material is based upon work performed by 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. Computational work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the US DOE under Contract 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
Subject Keywords:Solar Fuels; Bismuth Vanadate Photoanodes; combinatorial chemistry libraries; Computational materials science; Alloys
Issue or Number:9
Record Number:CaltechAUTHORS:20180423-104401758
Persistent URL:
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86009
Deposited By: Tony Diaz
Deposited On:25 Apr 2018 18:10
Last Modified:12 Aug 2021 23:40

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