Selective Semihydrogenation of Alkynes on Shape-Controlled Palladium Nanocrystals

A systematic study on the selective semihydrogenation of alkynes to alkenes on shape-controlled palladium (Pd) nanocrystals was performed. Pd nanocrystals with a cubic shape and thus exposed {100} facets were synthesized in an aqueous solution through the reduction of Na2PdCl4 with L-ascorbic acid in the presence of bromide ions. The Pd nanocubes were tested as catalysts for the semihydrogenation of various alkynes such as 5-decyne, 2-butyne-1,4-diol, and phenylacetylene. For all substrates, the Pd nanocubes exhibited higher alkene selectivity (>90%) than a commercial Pd/C catalyst (7590%), which was attributed to a large adsorption energy of the carboncarbon triple bond on the {100} facets of the Pd nanocubes. Our approach based on the shape control of Pd nanocrystals offers a simple and effective route to the development of a highly selective catalyst for alkyne semihydrogenation.