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Electrochemical Stability of Metastable Materials

Singh, Arunima K. and Zhou, Lan and Shinde, Aniketa and Suram, Santosh K. and Montoya, Joseph H. and Winston, Donald and Gregoire, John M. and Persson, Kristin A. (2017) Electrochemical Stability of Metastable Materials. Chemistry of Materials, 29 (23). pp. 10159-10167. ISSN 0897-4756. doi:10.1021/acs.chemmater.7b03980.

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We present a first-principles-based formalism to provide a quantitative measure of the thermodynamic instability and propensity for electrochemical stabilization, passivation, or corrosion of metastable materials in aqueous media. We demonstrate that this formalism can assess the relative Gibbs free energy of candidate materials in aqueous media as well as their decomposition products, combining solid and aqueous phases, as a function of pH and potential. On the basis of benchmarking against 20 stable as well as metastable materials reported in the literature and also our experimental characterization of metastable triclinic-FeVO_4, we present quantitative estimates for the relative Gibbs free energy and corresponding aqueous regimes where these materials are most likely to be stable, form inert passivating films, or steadily corrode to aqueous species. Furthermore, we show that the structure and composition of the passivating films formed on triclinic-FeVO_4 are also in excellent agreement with the Point Defect Model, as proposed by the corrosion community. An open-source web application based on the formalism is made available at

Item Type:Article
Related URLs:
URLURL TypeDescription Information
Singh, Arunima K.0000-0002-7212-6310
Zhou, Lan0000-0002-7052-266X
Shinde, Aniketa0000-0003-2386-3848
Suram, Santosh K.0000-0001-8170-2685
Montoya, Joseph H.0000-0001-5760-2860
Gregoire, John M.0000-0002-2863-5265
Persson, Kristin A.0000-0003-2495-5509
Additional Information:© 2017 American Chemical Society. Received: September 19, 2017; Revised: October 18, 2017; Published: October 24, 2017. This work was primarily funded 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 was additionally supported by the Materials Project (Grant No. EDCBEE) Predictive Modeling Center through the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Materials Sciences and Engineering Division, under Contract DE-AC02-05CH11231. Computational resources were provided by the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. The authors thank Matthias Richter for assistance with collection of XPS data. The authors declare no competing financial interest.
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
Department of Energy (DOE)DE-AC02-05CH11231
Issue or Number:23
Record Number:CaltechAUTHORS:20171024-154241789
Persistent URL:
Official Citation:Electrochemical Stability of Metastable Materials. Arunima K. Singh, Lan Zhou, Aniketa Shinde, Santosh K. Suram, Joseph H. Montoya, Donald Winston, John M. Gregoire, and Kristin A. Persson. Chemistry of Materials 2017 29 (23), 10159-10167. DOI: 10.1021/acs.chemmater.7b03980
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:82634
Deposited By: Tony Diaz
Deposited On:24 Oct 2017 22:53
Last Modified:15 Nov 2021 19:52

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