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Mechanistic insights into chemical and photochemical transformations of bismuth vanadate photoanodes

Toma, Francesca M. and Cooper, Jason K. and Kunzelmann, Viktoria and McDowell, Matthew T. and Yu, Jie and Larson, David M. and Borys, Nicholas J. and Abelyan, Christine and Beeman, Jeffrey W. and Yu, Kin Man and Yang, Jinhui and Chen, Le and Shaner, Matthew R. and Spurgeon, Joshua and Houle, Frances A. and Persson, Kristin A. and Sharp, Ian D. (2016) Mechanistic insights into chemical and photochemical transformations of bismuth vanadate photoanodes. Nature Communications, 7 . Art. No. 12012. ISSN 2041-1723. PMCID PMC4935965. doi:10.1038/ncomms12012.

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Artificial photosynthesis relies on the availability of semiconductors that are chemically stable and can efficiently capture solar energy. Although metal oxide semiconductors have been investigated for their promise to resist oxidative attack, materials in this class can suffer from chemical and photochemical instability. Here we present a methodology for evaluating corrosion mechanisms and apply it to bismuth vanadate, a state-of-the-art photoanode. Analysis of changing morphology and composition under solar water splitting conditions reveals chemical instabilities that are not predicted from thermodynamic considerations of stable solid oxide phases, as represented by the Pourbaix diagram for the system. Computational modelling indicates that photoexcited charge carriers accumulated at the surface destabilize the lattice, and that self-passivation by formation of a chemically stable surface phase is kinetically hindered. Although chemical stability of metal oxides cannot be assumed, insight into corrosion mechanisms aids development of protection strategies and discovery of semiconductors with improved stability.

Item Type:Article
Related URLs:
URLURL TypeDescription CentralArticle
Toma, Francesca M.0000-0003-2332-0798
Cooper, Jason K.0000-0002-7953-4229
Kunzelmann, Viktoria0000-0002-4225-0476
McDowell, Matthew T.0000-0001-5552-3456
Larson, David M.0000-0001-9634-9175
Borys, Nicholas J.0000-0001-5434-1191
Beeman, Jeffrey W.0000-0002-5678-6255
Shaner, Matthew R.0000-0003-4682-9757
Spurgeon, Joshua0000-0002-2987-0865
Houle, Frances A.0000-0001-5571-2548
Persson, Kristin A.0000-0003-2495-5509
Sharp, Ian D.0000-0001-5238-7487
Additional Information:© 2016 Macmillan Publishers Limited. This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit Received 01 January 2016; Accepted 20 May 2016; Published 05 July 2016. 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. Imaging 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 number DE-AC02-05CH11231. The EC-AFM part of this work was supported in part by the Laboratory Directed Research and Development Program of Lawrence Berkeley National Laboratory under U.S. Department of Energy contract number DE-AC02-05CH11231. V.K. and F.M.T. acknowledge support from the BaCaTeC programme, project number 2015-1. Craig Jones from Agilent Technologies, Inc. is greatly acknowledged for his help with ICP-MS measurements. Author contributions: F.M.T., F.A.H. and I.D.S. conceived of and designed this study. F.M.T., J.K.C., V.K., M.T.M., D.L., C.A., J.W.B. and I.D.S. performed the experiments. F.M.T., J.K.C., N.J.B., K.M.Y., J. Yang, F.A.H. and I.D.S. analysed and interpreted the data. J. Yu and K.A.P. performed the theoretical calculations and associated analysis. L.C., M.R.S. and J.S. provided some of the materials used for preliminary testing. All authors contributed to the final version of the manuscript. Competing financial interests: The authors declare no competing financial interests.
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
Department of Energy (DOE)DE-AC02-05CH11231
BaCaTeC programme2015-1
PubMed Central ID:PMC4935965
Record Number:CaltechAUTHORS:20160718-095141596
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Official Citation:Toma, F. M. et al. Mechanistic insights into chemical and photochemical transformations of bismuth vanadate photoanodes. Nat. Commun. 7:12012 doi: 10.1038/ncomms12012 (2016)
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:69089
Deposited By: Tony Diaz
Deposited On:19 Jul 2016 22:06
Last Modified:26 Apr 2022 17:16

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