Reactivity of Perovskites with Water: Role of Hydroxylation in Wetting and Implications for Oxygen Electrocatalysis

Oxides are instrumental to applications such as catalysis, sensing, and wetting, where the reactivity with water can greatly influence their functionalities. We find that the coverage of hydroxyls (*OH) measured at fixed relative humidity trends with the electron-donor (basic) character of wetted pe...

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Bibliographic Details
Main Authors: Biegalski, Michael D., Bluhm, Hendrik, Stoerzinger, Kelsey Ann, Hong, Wesley Terrence, Azimi, Gisele, Giordano, Livia, Lee, Yueh Lin, Crumlin, Ethan J, Varanasi, Kripa, Shao-Horn, Yang
Other Authors: Massachusetts Institute of Technology. Department of Electrical Engineering and Computer Science
Format: Article
Language:en_US
Published: American Chemical Society (ACS) 2017
Online Access:http://hdl.handle.net/1721.1/109598
https://orcid.org/0000-0003-1560-0749
https://orcid.org/0000-0003-2477-6412
https://orcid.org/0000-0002-6846-152X
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Summary:Oxides are instrumental to applications such as catalysis, sensing, and wetting, where the reactivity with water can greatly influence their functionalities. We find that the coverage of hydroxyls (*OH) measured at fixed relative humidity trends with the electron-donor (basic) character of wetted perovskite oxide surfaces. Using ambient pressure X-ray photoelectron spectroscopy, we report that the affinity toward hydroxylation, coincident with strong adsorption energies calculated for dissociated water and hydroxyl groups, leads to strong H bonding that is favorable for wetting while detrimental to catalysis of the oxygen reduction reaction (ORR). Our findings provide novel insights into the coupling between wetting and catalytic activity and suggest that catalyst hydrophobicity should be considered in aqueous oxygen electrocatalysis.