Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 136, Issue 16, Pages 6002-6010Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja413147e
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Funding
- DOE [DE-SC0009565]
- National Science Foundation [ECS-0335765]
- U.S. Department of Energy (DOE) [DE-SC0009565] Funding Source: U.S. Department of Energy (DOE)
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First-row metals have been a target for the development of oxygen evolution reaction (OER) catalysts because they comprise noncritical elements. We now report a comprehensive electrochemical characterization of manganese oxide (MnOx) over a wide pH range, and establish MnOx as a functionally stable OER catalyst owing to self-healing, is derived from MnOx redeposition that offsets catalyst dissolution during turnover. To study this process in detail, the oxygen evolution mechanism of MnOx was investigated electrokinetically over a pH range spanning acidic, neutral, and alkaline conditions. In the alkaline pH regime, a similar to 60 mV/decade Tafel slope and inverse first-order dependence on proton concentration were observed, whereas the OER acidic pH regime exhibited a quasi-infinite Tafel slope and zeroth-order dependence on proton concentration. The results reflect two competing mechanisms: a one-electron one-proton PCET pathway that is dominant under alkaline conditions and a Mn3+ disproportionation process, which predominates under acidic conditions. Reconciling the rate laws of these two OER pathways with that of MnOx electrodeposition elucidates the self-healing characteristics of these catalyst films. The intersection of the kinetic profile of deposition and that of water oxidation as a function of pH defines the region of kinetic stability for MnOx and importantly establishes that a non-noble metal oxide OER catalyst may be operated in acid by exploiting a self-healing process.
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