Assembling Giant Nanoclusters as Heterogeneous Catalysts for Effectively Converting CO2 to CO Under Visible Light

Abstract Heterometallic lanthanide‐transition metal (3d‐4f) nanoclusters with well‐defined structures and multiple active sites are excellent vehicles for achieving efficient catalysis and studying heterometallic synergism. In this work, two closely related yet different high‐nuclearity nanoclusters, 72‐nuclear {Ni 28 RE 44 } ( 1 , RE = Pr, Nd, Sm, Eu, and Gd) and 111‐nuclear {Ni 48 La 63 } ( 2 ), are synthesized using a mixed‐ligand strategy. Importantly, the crystal solids of these giant coordination clusters are insoluble when soaking in H 2 O/CH 3 CN and can be used as heterogeneous catalysts for visible‐light‐driven catalytic conversion of CO 2 to CO. Cluster 2 exhibits a maximum CO production rate of 4800 µmol g −1 h −1 and a CO selectivity of 92% over H 2 . Furthermore, the catalytic properties are investigated of different rare earths in the cluster 1 series, found that 1‐Eu exhibited superior catalytic performance under identical conditions, likely due to the lower reduction potential of the europium ions. This study represents the first report of 3d‐4f heterometallic nanoclusters as heterogeneous catalysts for photocatalytic reaction and provides a reference for the study of high‐nuclearity 3d‐4f nanoclusters as catalysts for photocatalytic reduction of CO 2 to CO.