Graduate School of Science, Technology, and Innovation, Kobe University, Kobe 657-8501, Japan.
Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810, Japan.
Phys Chem Chem Phys. 2022 Feb 16;24(7):4674-4682. doi: 10.1039/d1cp05816a.
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 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.
本研究考察了水合磷酸钴（CoPi）共催化剂的初始水氧化反应机制，该机制与传统的实验结果一致，涉及 O-O 键和 OOH 的形成。通过振动光谱计算验证的水合 CoPi 团簇模型的理论计算阐明了磷酸盐作为氧源和质子供体的作用，这两者导致在释放两个电子和两个质子后自发形成 O-O 键。计算还表明，OOH 的形成随后取决于水合 CoPi 表面的自旋电子态，并且在释放两个电子和两个质子后 O 的形成会自发进行。通过理论上追踪这些过程，提出了水合 CoPi 共催化剂的初始水氧化反应机制。
