Structure Sensitivity of the Oxygen Evolution Reaction Catalyzed by Cobalt(II,III) Oxide

化学 催化作用 析氧 氧化钴 无机化学 氧化物 氧气 物理化学 电化学 有机化学 电极
作者
Craig Plaisance,Rutger A. van Santen
出处
期刊:Journal of the American Chemical Society [American Chemical Society]
卷期号:137 (46): 14660-14672 被引量:128
标识
DOI:10.1021/jacs.5b07779
摘要

Quantum chemical calculations and simulated kinetics were used to examine the structure sensitivity of the oxygen evolution reaction on several surface terminations of Co3O4. Active sites consisting of two adjacent Co(IV) cations connected by bridging oxos were identified on both the (001) and (311) surfaces. Formation of the O–O bond proceeds on these sites by nucleophilic attack of water on a bridging oxo. It was found that the relative turnover frequencies for the different sites are highly dependent on the overpotential, with the dual-Co site on the (311) surface being most active at medium overpotentials (0.46−0.77 V), where O–O bond formation by water addition is rate limiting. A similar dual-Co site on the (001) surface is most active at low overpotentials (<0.46 V), where O2 release is rate limiting, and a single-Co site on the (110) surface is most active at overpotentials that are high enough (>0.77 V) to form a significant concentration of highly reactive terminal Co(V)═O species. Two overpotential-dependent Sabatier relationships were identified based on the Brønsted basicity and redox potential of the active site, explaining the change in the active site with overpotential. The (311) dual-Co site that is most active in the medium overpotential range is consistent with recent experimental observations suggesting that a defect site is responsible for the observed oxygen evolution activity and that a modest concentration of superoxo intermediates is present on the surface. Importantly, we find that it is essential to consider the kinetics of the water addition and O2 release steps rather than only the thermodynamics.
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