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Band Edge Energy Tuning through Electronic Character Hybridization in Ternary Metal Vanadates

Richter, Matthias H. and Peterson, Elizabeth A. and Zhou, Lan and Shinde, Aniketa A. and Newhouse, Paul F. and Yan, Qimin and Fackler, Sean W. and Yano, Junko and Cooper, Jason K. and Persson, Kristin A. and Neaton, Jeffrey B. and Gregoire, John M. (2021) Band Edge Energy Tuning through Electronic Character Hybridization in Ternary Metal Vanadates. Chemistry of Materials, 33 (18). pp. 7242-7253. ISSN 0897-4756. doi:10.1021/acs.chemmater.1c01415.

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In the search for photoanode materials with band gaps suitable for utilization in solar fuel generation, approximately 1.2–2.8 eV, theory-guided experiments have identified a variety of materials that meet the band gap requirements and exhibit operational stability in harsh photoelectrochemical environments. In particular, M-V-O compounds (M is a transition metal or main group element) with VO₄ structural motifs were predicted to show a remarkably wide range of band energetics (>3 eV variation in the energy of valence band maximum) and characteristics, depending on the M and crystal structure, which is beyond the extent of electronic structured tuning observed in previously studied families of metal oxide photoanodes. While this finding guided experimental discovery of new photoanode materials, explicit experimental verification of the theoretical prediction of the tunable electronic structure of these materials has been lacking to date. In this study, we use X-ray photoelectron spectroscopy and Kelvin probe microscopy to experimentally investigate the electronic structure of M-V-O photoanodes, enabling comparison to theory on a common absolute energy scale. The results confirm the prediction that band edge energies of ternary vanadates vary significantly with metal cations. The valence band variation of approximately 1 eV observed here is larger than that reported in any analogous class of metal oxide semiconductors and demonstrates the promise of tuning the metal oxide electronic structure to enable efficient photoelectrocatalysis of the oxygen evolution reaction and beyond. Because midgap states can hamper realization of the high photovoltage sought by band edge tuning, we analyze the electronic contributions of oxygen vacancies for the representative photoanode V₄Cr₂O₁₃ to guide future research on the development of high-efficiency metal oxide photoanodes for solar fuel technology.

Item Type:Article
Related URLs:
URLURL TypeDescription
Richter, Matthias H.0000-0003-0091-2045
Peterson, Elizabeth A.0000-0001-5379-3604
Zhou, Lan0000-0002-7052-266X
Shinde, Aniketa A.0000-0003-2386-3848
Newhouse, Paul F.0000-0003-2032-3010
Yano, Junko0000-0001-6308-9071
Cooper, Jason K.0000-0002-7953-4229
Persson, Kristin A.0000-0003-2495-5509
Neaton, Jeffrey B.0000-0001-7585-6135
Gregoire, John M.0000-0002-2863-5265
Additional Information:© 2021 The Authors. Published by American Chemical Society. Received: April 23, 2021; Revised: August 12, 2021; Published: September 13, 2021. The band character calculations and band energy experiments were supported by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the US DOE (Award DE-SC0004993). Defect energy calculations and analysis of associated experimental data were supported 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 Number DE-SC0021266. Research was in part carried out at the Molecular Materials Research Center in the Beckman Institute of the California Institute of Technology. This research used resources of the Advanced Light Source, a U.S. DOE Office of Science User Facility under contract no. DE-AC02-05CH11231. We acknowledge computational resources provided by the National Energy Research Scientific Computing Center (NERSC), supported by the Office of Science of the Department of Energy under Award No. DE-AC02-05CH11231. The authors declare no competing financial interest.
Group:JCAP, Liquid Sunlight Alliance
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
Department of Energy (DOE)DE-SC0021266
Department of Energy (DOE)DE-AC02-05CH11231
Issue or Number:18
Record Number:CaltechAUTHORS:20210917-215611668
Persistent URL:
Official Citation:Band Edge Energy Tuning through Electronic Character Hybridization in Ternary Metal Vanadates. Matthias H. Richter, Elizabeth A. Peterson, Lan Zhou, Aniketa A. Shinde, Paul F. Newhouse, Qimin Yan, Sean W. Fackler, Junko Yano, Jason K. Cooper, Kristin A. Persson, Jeffrey B. Neaton, and John M. Gregoire. Chemistry of Materials 2021 33 (18), 7242-7253; DOI: 10.1021/acs.chemmater.1c01415
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:110945
Deposited By: George Porter
Deposited On:20 Sep 2021 14:52
Last Modified:04 Oct 2021 17:34

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