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Fe Substitutions Improve Spectral Response of Bi₂WO₆-Based Photoanodes

Zhou, Lan and Peterson, Elizabeth A. and Richter, Matthias H. and Lai, Yungchieh and Neaton, Jeffrey B. and Gregoire, John M. (2022) Fe Substitutions Improve Spectral Response of Bi₂WO₆-Based Photoanodes. ACS Applied Energy Materials, 5 (12). pp. 15333-15344. ISSN 2574-0962. doi:10.1021/acsaem.2c02964.

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The quest for a scalable solar fuel technology has stimulated a concerted effort to develop a metal oxide semiconductor for solar-driven photoelectrochemical water oxidation (oxygen evolution reaction) in an efficient and durable manner. So far, the search for such a metal oxide photoanode has highlighted the promise of Bi-based oxides, which have also been extensively studied for other photocatalyst applications. Bi₂WO₆ is a durable photocatalyst whose primary shortcoming is a 2.8 eV band gap that limits utilization of the solar spectrum. Improvements in visible photoresponse upon incorporation of Fe have been reported in the photocatalysis literature, motivating our use of high-throughput synthesis and photoelectrochemistry to determine the spectral photoresponse for Bi–W–Fe oxides synthesized under nonequilibrium conditions based on thermal oxidation of metallic films. Photoactivity down to 2 eV was achieved over a broad range of compositions, with detailed characterization of optimal compositions revealing that Fe incorporation increases the valence band position by 0.75 eV. Density functional theory calculations of Fe substitutions on W sites in Bi₂WO₆ re consistent with this valence band shift, providing a plausible explanation for the experiments. This Fe-mediated band tuning yields a ca. 2 eV band gap while retaining a turn-on potential for photoanodic current near 0.4 V versus RHE, which combined with the operational durability motivates continuous study and development of this promising class of metal oxide photoanodes.

Item Type:Article
Related URLs:
URLURL TypeDescription
Zhou, Lan0000-0002-7052-266X
Peterson, Elizabeth A.0000-0001-5379-3604
Richter, Matthias H.0000-0003-0091-2045
Lai, Yungchieh0000-0001-9392-1447
Neaton, Jeffrey B.0000-0001-7585-6135
Gregoire, John M.0000-0002-2863-5265
Additional Information:This material is based on work performed by the Liquid Sunlight Alliance, which is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Fuels from Sunlight Hub under Award DE-SC0021266. Computational resources were provided by the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy Office of Science User Facility located at Lawrence Berkeley National Laboratory (LBNL) under contract no. DE-AC02-05CH11231. Additional computing resources were provided by the Lawrencium computational cluster at LBNL under the same contract number. The authors thank Aniketa Shinde for assistance with PEC experiments and Paul Newhouse for assistance with optical spectroscopy.
Group:Liquid Sunlight Alliance
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0021266
Department of Energy (DOE)DE-AC02-05CH11231
Issue or Number:12
Record Number:CaltechAUTHORS:20230123-451320900.13
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:118888
Deposited By: Research Services Depository
Deposited On:16 Feb 2023 17:52
Last Modified:16 Feb 2023 17:52

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