Do multinuclear 3d metal catalysts achieve O-O bond formation via radical coupling or via water nucleophilic attack? WNA leads the way in [Co₄O₄]ⁿ.

ABSTRACT: Catalytic water oxidation is a required process for clean energy production based on the concept of artificial photosynthesis. Here, we provide in situ spectroscopic and computational analysis for the closest known photosystem II analog, [Co₄O₄]ⁿ⁺ ([Co₄O₄Py₄Ac₄]⁰, Py = pyridine and Ac = CH₃COO^-), which catalyzes electrochemical water oxidation. In situ extended X-ray absorption fine structure detects an ultrashort, Co^IV=O (~1.67 Å) moiety, a crucial intermediate for O-O bond formation. Density function theory analyses show that the intermediate has two Co^IV centers and a Co^IV=O unit of strong radicaloid character sufficient to support

SUBMITTER: Ezhov R 

PROVIDER: S-EPMC10296785 | biostudies-literature | 2021 Jul

REPOSITORIES: biostudies-literature