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Published August 30, 2023 | v1
Journal Article Open

Understanding the Catalytic Active Sites of Crystalline CoSbₓOᵧ for Electrochemical Chlorine Evolution

Abstract

The chlorine evolution reaction (CER) is a key reaction in electrochemical oxidation (EO) of water treatment. Conventional anodes based on platinum group metals can be prohibitively expensive, which hinders further application of EO systems. Crystalline cobalt antimonate (CoSbO) was recently identified as a promising alternative to conventional anodes due to its high catalytic activity and stability in acidic media. However, its catalytic sites and reaction mechanism have not yet been elucidated. This study sheds light on the catalytically active sites in crystalline CoSbO anodes by using scanning electrochemical microscopy to compare the CER catalytic activities of a series of anode samples with different bulk Sb/Co ratios (from 1.43 to 2.80). The results showed that Sb sites served as more active catalytic sites than the Co sites. The varied Sb/Co ratios were also linked with slightly different electronic states of each element, leading to different CER selectivities in 30 mM chloride solutions under 10 mA cm⁻² current density. The high activity of Sb sites toward the CER highlighted the significance of the electronic polarization that changed the oxidation states of Co and Sb.

Copyright and License

© 2023 The Authors. Published by American Chemical Society. Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).

Acknowledgement

The authors acknowledge generous financial support from the Bill and Melinda Gates Foundation (grant no. INV047212), supporting H.D., S.T.M., and M.R.H. This work was also supported by the Stanford Doerr School of Sustainability Accelerator. SECM measurements (X.S., W.A.T.) were supported by the Department of Energy, Laboratory Directed Research and Development program at SLAC National Accelerator Laboratory, under contract DE-AC02-76SF00515. Part of this work was performed at the Stanford Nano Shared Facilities (SNSF), supported by the National Science Foundation under award ECCS-2026822. The Massachusetts Department of Transportation (MassDOT) Highway Division under Interagency Service Agreement no. 87790 with the University of Massachusetts Amherst funded S.H. The views, opinions, and findings in this study are those of the authors and do not reflect MassDOT official views or policies.

Contributions

H.D. and X.S. contributed equally to this paper.

Conflict of Interest

The authors declare no competing financial interest.

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Additional details

Created:
September 6, 2023
Modified:
September 6, 2023