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The possibility of using inner cavities within metal-organic frameworks (MOFs) as templates for the fabrication of tiny metal nanoparticles (NPs) was attempted in this work. An unprecedented design of Pd@Ag core-shell NPs on MOFs via a seed mediated growth strategy is reported and attributed to the presence of activated physisorbed hydrogen atoms on embedded Pd NPs as reducing agents to selectively direct the deposition of Ag onto Pd while minimizing the Ag self-nucleation. The obtained Pd@Ag core-shell NPs exhibited a significant increase in selectivity in the partial hydrogenation of phenylacetylene as compared to their monometallic counterparts, due to the surface dilution and electron modification of the surface Pd sites by Ag deposition. Pd@Ag NPs also possessed an unprecedented high stability and recyclability in the catalytic reactions, related to the nano-confinement effect and the strong metal-support interaction offered by the MOF framework.

Seed-mediated growth of MOF-encapsulated Pd@Ag core–shell nanoparticles: toward advanced room temperature nanocatalysts