Pairwise Stereoselective Hydrogenation of Propyne on Supported Pd–Ag Catalysts Investigated by Parahydrogen-Induced Polarization

Abstract

Alkyne semihydrogenation offers a key approach for the synthesis of stereodefined molecules. The stereoselective hydrogenation of propyne to propene over Al2O3-supported Pd–Ag bimetallic catalysts is studied by using parahydrogen-induced polarization (PHIP) NMR technique. The supported catalysts were prepared by an incipient-wetness impregnation method, and their properties were systemically tuned by altering Pd and Ag components. Structural characterization by X-ray diffraction, infrared spectra, and transmission electron microscope shows the formation of highly dispersed bimetallic Pd–Ag nanoparticles with random alloy structures on Al2O3 support. For the hydrogenation of propyne over Pd–Ag catalysts with higher Ag concentration, the adsorbed protons are mostly restricted on the active Pd ensembles, which favors a higher pairwise hydrogen addition to propyne, leading to a stronger PHIP effect. The product stereoselectivity measurements show that the pairwise syn-addition to propyne increases with Ag content in the Pd–Ag alloy. The reaction conditions impact the pairwise hydrogenation stereoselectivity. A lower H2/propyne ratio of reactant flow or a higher total reactant flow rate enhances the apparent pairwise syn-addition stereoselectivity, which can be accounted for by the suppressed cis–trans isomerization process and/or a higher intrinsic pairwise syn-addition selectivity.