Developing Insoluble Polyoxometalate Clusters to Bridge Homogeneous and Heterogeneous Water Oxidation Photocatalysis

• Published in: Angewandte Chemie International Edition 2023-08, Vol.62 (32), p.e202303290-n/a
• Main Authors: Hu, Qiyu, Chen, Shoushun, Wågberg, Thomas, Zhou, Hongshan, Li, Shujun, Li, Yiding, Tan, Yilan, Hu, Wenqi, Ding, Yong, Han, Xinbao
• Format: Article
• Language: English
• Subjects: Catalysis; Catalysts; Cations; Cerium; Cluster-Based Solid Catalysts; Cobalt; Diffraction patterns; Electron microscopy; Electron transfer; Flash photolysis; Fourier transforms; Infrared spectroscopy; Lead; Oxidation; Photocatalysis; Photoelectron spectroscopy; Photoelectrons; Photolysis; Polyoxometallates; Raman spectroscopy; Recyclability; Spectrum analysis; Stability; Structure–Activity Relationships; Water Oxidation
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202303290

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. A series of cobalt(II)‐containing polyoxometalate (POM) cluster‐based solid catalysts were synthesized with different counter‐cations and applied to photocatalytic water oxidation. Candidates in the series bridge homogeneous and heterogeneous catalysts by offering activity comparable to the parent homogeneous catalyst and good recyclability.