Converting metal–organic polyhedra to Pd single atoms on graphene for efficient selective semi‐hydrogenation of alkynes

Abstract Selective hydrogenation of alkynes to alkenes is pivotal in the chemical industry. Pd‐containing materials have been proven to be effective catalysts, while balancing the activity‐selectivity trade‐off remains a significant challenge. Here we report the fabrication of Pd single atoms from the conversion of metal–organic polyhedra (MOPs) for the first time. The MOP (M 6 L 4 ), constructed from Pd salt and N‐containing ligand, can interact with the graphene support via π‐electron coupling, leading to well dispersion of MOP molecules. In subsequent thermal treatment, Pd is anchored by N‐doped graphene formed in situ, producing single Pd atoms (denoted as Pd 1 /G). The obtained Pd 1 /G catalyst exhibits excellent activity (100% conversion) and styrene selectivity (94%) in the semi‐hydrogenation of phenylacetylene under mild conditions (298 K, 1 bar H 2 ). Such performance is much superior to the counterpart catalyst Pd/G with Pd nanoparticles and the commercial Lindlar catalyst and is among the best of the reported catalysts for phenylacetylene semi‐hydrogenation.