Isolated Effects of Surface Ligand Density on the Catalytic Activity and Selectivity of Palladium Nanoparticles

Alkanethiolate-capped palladium nanoparticles (PdNPs) have previously been synthesized by using a modified Brust–Schiffrin synthesis (using alkanethiosulfate instead of alkanethiol), in which the nanoparticle core size is established during alkanethiosulfate ligand passivation of the nanoparticle nucleation–growth initiated by borohydride reduction. Because of the dependence of core size on the amount of ligand present, surface ligand density decreases with increasing core size. Herein we present a method in which the core size is established independent of ligand addition, allowing the formation of PdNPs with similar core sizes yet different surface ligand densities. In this method, the core size is established during the temporary passivation of growing nanoparticles by borohydride and tetra-N-octylammonium bromide (TOAB), allowing nucleation to reach completion. Various molar equivalents of alkyl thiosulfate are then added, prompting the replacement of borohydride and TOAB and the formation of alkanethiolate-capped PdNPs. The resulting PdNPs were characterized by using ¹H NMR, transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and inductively coupled plasma atomic emission spectroscopy (ICP-AES). The overall enhanced catalytic activity of hydrogenation/isomerization of alkenes and dienes was observed for PdNPs with a lower ligand density, proving the isolated effect of surface ligand density from other variations such as core size and shape. Surface ligand density is also shown to influence the hydrogenation/isomerization product selectivity of the catalytic reactions by regulating the formation of certain Pd–substrate intermediates and the kinetic diffusion of surface hydrogen/substrates.