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

Single Ru atoms and triatomic Ru₃ clusters confined in functionalized ZIF‐8 as composite catalysts combine the advantages of atomically dispersed Ru species and a microporous MOF structure. This facilitates highly efficient and selective catalysis for the partial hydrogenation of alkynes. Size‐dependent performance between Ru₃@ZIF‐8 and Ru₁@ZIF‐8 catalysts is revealed.

Abstract

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 Ru₃ clusters anchored on ZIF‐8 (Ru₁@ZIF‐8, Ru₃@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 Ru₃@ZIF‐8 and Ru₁@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.

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