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Quaternary Oxide Photoanode Discovery Improves the Spectral Response and Photovoltage of Copper Vanadates

Zhou, Lan and Shinde, Aniketa and Newhouse, Paul F. and Guevarra, Dan and Wang, Yu and Lai, Yungchieh and Kan, Kevin and Suram, Santosh K. and Haber, Joel A. and Gregoire, John M. (2020) Quaternary Oxide Photoanode Discovery Improves the Spectral Response and Photovoltage of Copper Vanadates. Matter, 3 (5). pp. 1614-1630. ISSN 2590-2385. doi:10.1016/j.matt.2020.08.031.

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Copper vanadates are a promising class of solar fuel photoanodes with broad spectral response and excellent operational stability. The present performance limitations of these photoanodes are most evident in the rapid decrease in photoactivity with decrease in either photon energy or applied bias, the former limiting efficient utilization of the solar spectrum and the latter limiting photovoltage. We designed high-throughput photoelectrochemical screening to characterize these two aspects of improving Cu-V-based photoanodes in quaternary oxide composition spaces of the form Cu-V-X-O, where X = Mg, Ca, Sr, Fe. The results reveal that alloying of 2+ cations onto the Cu site of copper vanadates can improve photoelectrochemical properties, and Sr-alloyed Cu₅V₂O₁₀ emerges as the most promising photoanode providing the best combination of photovoltage and spectral response. Six quaternary oxide phases are discovered as photoanodes with visible light activity below 1.23 V versus reversible hydrogen electrode, highlighting the high-throughput photoanode discovery.

Item Type:Article
Related URLs:
URLURL TypeDescription
Zhou, Lan0000-0002-7052-266X
Shinde, Aniketa0000-0003-2386-3848
Newhouse, Paul F.0000-0003-2032-3010
Guevarra, Dan0000-0002-9592-3195
Wang, Yu0000-0003-3589-9274
Lai, Yungchieh0000-0001-9392-1447
Suram, Santosh K.0000-0001-8170-2685
Haber, Joel A.0000-0001-7847-5506
Gregoire, John M.0000-0002-2863-5265
Additional Information:© 2020 Elsevier. Received 3 July 2020, Revised 8 August 2020, Accepted 27 August 2020, Available online 1 October 2020. This study 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 (award DE-SC0004993). Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under contract DEAC02-76SF00515. The authors thank Douglas van Campen and Apurva Mehta for assistance with synchrotron XRD measurements. Author Contributions. L.Z. synthesized the composition libraries, collected and analyzed the composition (XRF) and crystal structure (XRD) data, and performed data analysis and visualization. A.S., Y.W., Y.L., and K.K. collected and A.S., L.Z., and D.G. analyzed the PEC data. D.G. also developed data analysis and visualization algorithms. P.F.N. collected and analyzed the optical data. S.K.S., L.Z., and J.M.G. designed the composition spaces for exploration and performed synchrotron XRD measurements. J.M.G. also supervised the project and participated in data analysis and interpretation. L.Z. and J.M.G. wrote the manuscript with contributions from J.A.H. and input from each author. The authors declare no competing interests.
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
Department of Energy (DOE)DE-AC02-76SF00515
Subject Keywords:solar fuels; oxygen evolution reaction (OER); photoanode; copper vanadates; quaternary metal oxides; photoelectrochemistry; high-throughput experimentation
Issue or Number:5
Record Number:CaltechAUTHORS:20201002-151459149
Persistent URL:
Official Citation:Lan Zhou, Aniketa Shinde, Paul F. Newhouse, Dan Guevarra, Yu Wang, Yungchieh Lai, Kevin Kan, Santosh K. Suram, Joel A. Haber, John M. Gregoire, Quaternary Oxide Photoanode Discovery Improves the Spectral Response and Photovoltage of Copper Vanadates, Matter, Volume 3, Issue 5, 2020, Pages 1614-1630, ISSN 2590-2385, (
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:105772
Deposited By: George Porter
Deposited On:05 Oct 2020 14:39
Last Modified:16 Nov 2021 18:46

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