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The Restructuring-Induced CoO _x Catalyst for Electrochemical Water Splitting.

ABSTRACT: Restructuring is an important yet less understood phenomenon in the catalysis community. Recent studies have shown that a group of transition metal sulfide catalysts can completely or partially restructure during electrochemical reactions which then exhibit high activity even better than the best commercial standards. However, such restructuring processes and the final structures of the new catalysts are elusive, mainly due to the difficulty from the reaction-induced changes that cannot be captured by ex situ characterizations. To establish the true structure-property relationship in these in situ generated catalysts, we use multimodel operando characterizations including Raman spectroscopy, X-ray absorption spectroscopy, and X-ray reflectivity to investigate the restructuring of a representative catalyst, Co₉S₈, that shows better activity compared to the commercial standard RuO₂ during the oxygen evolution reaction (OER), a key half reaction in water-splitting for hydrogen generation. We find that Co₉S₈ ultimately converts to oxide cluster (CoO _x ) containing six oxygen coordinated Co octahedra as the basic unit which is the true catalytic center to promote high OER activity. The density functional theory calculations verify the in situ generated CoO _x consisting of edge-sharing CoO₆ octahedral clusters as the actual active sites. Our results also provide insights to design other transition-metal-based materials as efficient electrocatalysts that experience a similar restructuring in OER.

SUBMITTER: Wang M

PROVIDER: S-EPMC8715481 | biostudies-literature |

REPOSITORIES: biostudies-literature

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