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.