Identifying Metal-Oxo/Peroxo Intermediates in Catalytic Water Oxidation by In Situ Electrochemical Mass Spectrometry

• DOI: 10.1021/jacs.2c07026
• Publication Date: 2022-09-23T13:44:51Z
• Authors: Xianhao Zhang; Qi-Fa Chen; Jintao Deng; Xinyu Xu; Jirui Zhan; Hao-Yi Du; Zhengyou Yu; Meixian Li; Ming-Tian Zhang; Yuanhua Shao
• Keywords: Reaction intermediate

Molecular catalysis of water oxidation has been intensively investigated, but its mechanism is still not yet fully understood. This study aims at capturing and identifying key short-lived intermediates directly during the catalyzed by a cobalt-tetraamido macrocyclic ligand complex using newly developed an in situ electrochemical mass spectrometry (EC-MS) method. Two ligand-centered-oxidation intermediates, [(L2–)CoIIIOH] [(L2–)CoIIIOOH], were observed for first time, further confirmed 18O-labeling collision-induced dissociation studies. These experimental results rationality nucleophilic attack single-site catalysis. work also demonstrated that such EC-MS method promising analytical tool redox catalytic processes, only limited to oxidation.