Isomorphous Substitution of Organic Cage Crystal by Pd Nanoclusters for Selective Hydrogenation.

For supporting active metal, the cavity confinement and mass transfer facilitation lie not in one sack, a trade-off between high activity and good stability of the catalyst is present. Porous organic cages (POCs) are expected to break the trade-off when metal particles are properly loaded. Herein, three organic cages (CC3, RCC3, and FT-RCC3) are employed to support Pd nanoclusters for catalytic hydrogenation. Subnanometer Pd clusters locate differently in different cage frameworks by using the same reverse double-solvents approach. Compared with those encapsulated in the intrinsic cavity of RCC3 and anchored on the outer surface of CC3, the Pd nanoclusters orderly assembled in FT-RCC3 crystal via isomorphous substitution exhibit superior activity, high selectivity, and good stability for semi-hydrogenation of phenylacetylene. Isomorphous substitution of FT-RCC3 crystal by Pd nanoclusters is originated from high crystallization capacity of FT-RCC3 and specific interaction of each Pd nanocluster with four cage windows. Both confinement function and H 2 accumulation capacity of FT-RCC3 are fully utilized to support active Pd nanoclusters for efficient selective hydrogenation. The present results provide a new perspective to the heterogeneous catalysis field in terms of crystalizing metal nanoclusters in POC framework and outside the cage for making the best use of both parts.