open access

https://hdl.handle.net/2115/88184

Water-oxidation mechanism of cobalt phosphate co-catalyst in artificial photosynthesis : a theoretical study

英語

2022-02-02

Royal Society of Chemistry

Physical chemistry chemical physics

24(7)

4674-4682

The initial water-oxidation reaction mechanism of the hydrated cobalt phosphate (CoPi) co-catalyst, which is consistent with conventional experimental findings, is investigated for O-O bond and OOH formation in this study. Theoretical calculations of hydrated CoPi cluster models, which are validated by vibrational spectrum calculations, elucidate the roles of phosphate as a source of oxygen and deliverer of protons, both of which result in the spontaneous formation of an O-O bond after the release of two electrons and two protons. The calculations also show that OOH formation proceeds subsequently depending on the spin electronic states of the hydrated CoPi surface, and O-2 formation then spontaneously progresses after the release of two electrons and two protons. By theoretically tracing these processes, the initial water-oxidation reaction mechanism of the hydrated CoPi co-catalyst is proposed.

学術雑誌論文

Accepted Manuscript

1463-9076