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Cluster catalysts are attractive for their atomically precise structures, defined compositions, tunable coordination environments, uniform active sites, and their ability to transfer multiple electrons, but they suffer from poor stability and recyclability. Here, we report a general approach to the direct insolubilization of a water soluble polyoxometalate (POM) [{(B‐α‐PW9O34)Co3(OH)(H2O)2(O3PC(O)‐(C3H6NH3)PO3)}2Co]14− (Co7) and formation of a series of POM‐based solid catalysts with the counter‐cations Ag+, Cs+, Sr2+, Ba2+, Pb2+, Y3+, and Ce3+. They exhibit improved catalytic activities for visible‐light‐driven water oxidation following the trend CsCo7>SrCo7>AgCo7>CeIIICo7>BaCo7>YCo7>PbCo7. While CsCo7 exhibits mainly homogeneous catalysis, the others are predominantly heterogeneous catalysts. An optimal oxygen yield of 41.3 % and a high apparent quantum yield (AQY) of 30.6 % for SrCo7 is obtained, which is comparable to that of the parent homogeneous POM. Band gap structures, UV/Vis spectra, and real‐time laser flash photolysis experiments collectively suggest that easier electron transfer from the solid POM catalyst to the photosensitizer promotes photocatalytic water oxidation performance. These solid POM catalysts exhibit good stability, which is directly confirmed by a combination of Fourier‐transform infrared spectroscopy, electron microscopy, X‐ray diffraction patterns, Raman spectroscopy, X‐ray photoelectron spectroscopy, five cycles of tests, and poisoning experiments. [ABSTRACT FROM AUTHOR]

Keywords: Cluster-Based Solid Catalysts; Cobalt; Photocatalysis; Structure-Activity Relationships; Water Oxidation EN Cluster-Based Solid Catalysts Cobalt Photocatalysis Structure-Activity Relationships Water Oxidation 1 1 1 08/02/23 20230807 NES 230807 B Polyoxometalates b . Cluster-Based Solid Catalysts, Cobalt, Photocatalysis, Structure-Activity Relationships, Water Oxidation In their Research Article (e202303290), Yong Ding, Xinbao Han et al. report the synthesis of a series of cobalt(II)-containing polyoxometalate-based catalysts and their application to photocatalytic water oxidation. [Extracted from the article]