Atomically Dispersed Ruthenium Species Inside Metal-Organic Frameworks: Combining the High Activity of Atomic Sites and the Molecular Sieving Effect of MOFs.

Incorporating atomically dispersed metal species into functionalized metal-organic frameworks (MOFs) can integrate their respective merits for catalysis. A cage-controlled encapsulation and reduction strategy is used to fabricate single Ru atoms and triatomic Ru clusters anchored on ZIF-8 (Ru @ZIF-8, Ru @ZIF-8). The highly efficient and selective catalysis for semi-hydrogenation of alkyne is observed. The excellent activity derives from high atom-efficiency of atomically dispersed Ru active sites and hydrogen enrichment by the ZIF-8 shell. Meanwhile, ZIF-8 shell serves as a novel molecular sieve for olefins to achieve absolute regioselectivity of catalyzing terminal alkynes but not internal alkynes. Moreover, the size-dependent performance between Ru @ZIF-8 and Ru @ZIF-8 is detected in experiment and understood by quantum-chemical calculations, demonstrating a new and promising approach to optimize catalysts by controlling the number of atoms.