Core‐Shell‐Type All‐Inorganic Heterometallic Nanoclusters: Record High‐Nuclearity Cobalt Polyoxoniobates for Visible‐Light‐Driven Photocatalytic CO2 Reduction

Only rarely have polyoxometalates been found to form core–shell nanoclusters. Here, we succeeded in isolating a series of rare giant and all‐inorganic core–shell cobalt polyoxoniobates (Co−PONbs) with diverse shapes, nuclearities and original topologies, including 50‐nuclearity {Co12Nb38O132}, 54‐nu...

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Published in:Angewandte Chemie International Edition 2023-06, Vol.62 (26), p.e202305260-n/a
Main Authors: Guo, Zheng‐Wei, Lin, Ling‐Hui, Ye, Jian‐Ping, Chen, Yi, Li, Xin‐Xiong, Lin, Sen, Huang, Jian‐Dong, Zheng, Shou‐Tian
Format: Article
Language:English
Subjects:
Bimetals
Carbon dioxide
Catalysts
CO2 Reduction
Cobalt
Cobalt oxides
Cores
Core–Shell
High-Nuclearity
Molecular modelling
Nanoclusters
Polyoxometallates
Polyoxoniobate
Reduction
Spinel
Topology
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Summary:Only rarely have polyoxometalates been found to form core–shell nanoclusters. Here, we succeeded in isolating a series of rare giant and all‐inorganic core–shell cobalt polyoxoniobates (Co−PONbs) with diverse shapes, nuclearities and original topologies, including 50‐nuclearity {Co12Nb38O132}, 54‐nuclearity {Co20Nb34O128}, 62‐nuclearity {Co26Nb36O140} and 87‐nuclearity {Co33Nb54O188}. They are the largest Co−PONbs and also the polyoxometalates containing the greatest number of Co ions and the largest cobalt clusters known thus far. These molecular Co−PONbs have intriguing and atomically precise core–shell architectures comprising unique cobalt oxide cores and niobate oxide shells. In particular, the encapsulated cobalt oxide cores with different nuclearities have identical compositions, structures and mixed‐valence Co3+/Co2+ states as the different sized Co−O moieties of the bulk cubic‐spinel Co3O4, suggesting that they can serve as various molecular models of the cubic‐spinel Co3O4. The successful construction of the series of the Co−PONbs reveals a feasible and versatile synthetic method for making rare core–shell heterometallic PONbs. Further, these new‐type core–shell bimetal species are promising cluster molecular catalysts for visible‐light‐driven CO2 reduction. A series of rare Co−Nb‐based core–shell polyoxometalates containing 50, 54, 62 and 87 metal polyhedra is prepared. The cobalt oxide cores correspond to increasingly large molecular analogues of infinite cubic‐spinel Co3O4. They are the largest cobalt polyoxoniobates and the polyoxometalates with the greatest number of Co ions and the highest‐nuclearity cobalt clusters known thus far. They are shown to be efficient photocatalysts for CO2 reduction.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202305260