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 {Co12 Nb38 O132 }, 54-nuclearity {Co20 Nb34 O128 }, 62-nuclearity {Co26 Nb36 O140 } and 87-nuclearity {Co33 Nb54 O188 }. 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 Co3 O4 , suggesting that they can serve as various molecular models of the cubic-spinel Co3 O4 . 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.