title: A Bioinspired Molecular Polyoxometalate Catalyst with Two Cobalt(II) Oxide Cores for Photocatalytic Water Oxidation.
abstract: To overcome the bottleneck of water splitting, the exploration of efficient, selective, and stable water oxidation catalysts (WOCs) is crucial. We report an all-inorganic, oxidatively and hydrolytically stable WOC based on a polyoxometalate [(A-α-SiW9 O34)2Co8(OH)6(H2O)2(CO3)3](16-) (Co8 POM). As a cobalt(II)-based cubane water oxidation catalyst, Co8POM embeds double Co(II)4O3 cores. The self-assembled catalyst is similar to the oxygen evolving complex (OEC) of photosystem II (PS II). Using [Ru(bpy)3](2+) as a photosensitizer and persulfate as a sacrificial electron acceptor, Co8POM exhibits excellent water oxidation activity with a turnover number (TON) of 1436, currently the highest among bioinspired catalysts with a cubical core, and a high initial turnover frequency (TOF). Investigation by several spectroscopy, spectrometry, and other techniques confirm that Co8POM is a stable and efficient catalyst for visible light-driven water oxidation. The results offer a useful insight into the design of water oxidation catalysts.
authors.affiliation: Key Laboratory of Nonferrous Metal Chemistry and Resources, Utilization of GanSu Province, State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (PR China).
authors.forename: Jie
authors.initials: J
authors.lastname: Wei
authors.affiliation: Key Laboratory of Nonferrous Metal Chemistry and Resources, Utilization of GanSu Province, State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (PR China).
authors.forename: Yingying
authors.initials: Y
authors.lastname: Feng
authors.affiliation: Key Laboratory of Nonferrous Metal Chemistry and Resources, Utilization of GanSu Province, State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (PR China).
authors.forename: Panpan
authors.initials: P
authors.lastname: Zhou
authors.affiliation: Key Laboratory of Nonferrous Metal Chemistry and Resources, Utilization of GanSu Province, State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (PR China).
authors.forename: Yan
authors.initials: Y
authors.lastname: Liu
authors.affiliation: Key Laboratory of Nonferrous Metal Chemistry and Resources, Utilization of GanSu Province, State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (PR China).
authors.forename: Jingyin
authors.initials: J
authors.lastname: Xu
authors.affiliation: Key Laboratory of Nonferrous Metal Chemistry and Resources, Utilization of GanSu Province, State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (PR China).
authors.forename: Rui
authors.initials: R
authors.lastname: Xiang
authors.affiliation: Key Laboratory of Nonferrous Metal Chemistry and Resources, Utilization of GanSu Province, State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (PR China). dingyong1@lzu.edu.cn.|State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (PR China). dingyong1@lzu.edu.cn.
authors.forename: Yong
authors.initials: Y
authors.lastname: Ding
authors.affiliation: Department of Chemistry, Northwestern University, Evanston, IL, 60201 (USA).
authors.forename: Chongchao
authors.initials: C
authors.lastname: Zhao
authors.affiliation: Key Laboratory of Cluster Science Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic, School of Chemistry, Beijing Institute of Technology, Beijing 100081 (PR China).
authors.forename: Linyuan
authors.initials: L
authors.lastname: Fan
authors.affiliation: Key Laboratory of Cluster Science Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic, School of Chemistry, Beijing Institute of Technology, Beijing 100081 (PR China).
authors.forename: Changwen
authors.initials: C
authors.lastname: Hu
mesh_terms: D040761:Biomimetic Materials; D002384:Catalysis; D003035:Cobalt / Q000737:chemistry* / Q000528:radiation effects; D056831:Coordination Complexes / Q000737:chemistry* / Q000528:radiation effects; D008027:Light; D009942:Organometallic Compounds / Q000737:chemistry / Q000528:radiation effects; D010084:Oxidation-Reduction; D010087:Oxides / Q000737:chemistry*; D055668:Photochemical Processes; D017319:Photosensitizing Agents / Q000737:chemistry / Q000528:radiation effects; D017973:Tungsten Compounds / Q000737:chemistry* / Q000528:radiation effects; D014867:Water / Q000737:chemistry; D000099294:Polyoxometalates
chemical_list: D003035:Cobalt; D056831:Coordination Complexes; D009942:Organometallic Compounds; D010087:Oxides; D017319:Photosensitizing Agents; D017973:Tungsten Compounds; D014867:Water; C102296:polyoxometalate I; D000099294:Polyoxometalates; C415768:tris(2,2'-bipyridyl)ruthenium(II)
keywords: cobalt; homogeneous catalysis; photocatalysis; polyoxometalates; water oxidation