Electronic structure and operando spectroscopic characterization of active sites in oxygen-evolving catalyst NiFe oxyhydroxide

Zachary Goldsmith, Ohio Supercomputer Center

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This project aims to characterize at a density functional theory level the likely active sites in the oxygen-evolving electrocatalyst NiFe oxyhydroxide. Such a characterization includes understanding the redox chemistry of the catalyst thin film, its metal oxidation states, as well the nature of the frontier bands in its electronic structure. The work described here involves edge-terminated Ni and NiFe oxyhydroxide films. Terminations of the film have been proven experimentally to be the sites at which catalytic intermediates are turned over, going through high Fe oxidation states in the process. These studies describe how the electronic structure responds to the broken periodicity of the film. In addition, Fe has been doped in to the film at both the interior and exterior layers. Novel results include the energetic preference for Fe at exterior sites, reliable metal oxidation states, and the characteristic sites expected to electrocatalytically active.