Ultrasmall Platinum Stabilized on Triphenylphosphine-Modified Silica for Chemoselective Hydrogenation

Graphical Stability from supports : Ultrasmall platinum nanoparticles (Pt NPs) stabilized by triphenylphosphine-modified Pt/SiO 2 show high activity and good selectivity in acetophenone and phenylacetylene hydrogenation reactions compared with those on bare Pt/SiO 2 because of strong metal–support interactions (see figure). Chemoselective hydrogenation of substrates with more than one functional group that could be hydrogenated is quite challenging and is of fundamental importance. Here, the enhanced chemoselectivity of ultrasmall (<1 nm) platinum nanoparticles (NPs) stabilized on silica modified with triphenylphosphine (PSiO 2 ) in hydrogenation reactions is reported. Platinum NPs on PSiO 2 exhibit much higher selectivity than those on SiO 2 in the hydrogenation of acetophenone to 1-phenylethanol (99.9 versus 36 %) and hydrogenation of phenylacetylene to styrene (85 versus 52 %). The results of NMR spectroscopy, X-ray photoelectron spectroscopy, and in situ CO adsorption FTIR spectroscopy indicate the existence of strong interactions between triphenylphosphine and Pt NPs. Consequently, Pt NPs on PSiO 2 have smaller particle sizes and more positive Pt 4 f binding energy than those of Pt/SiO 2 ; these are the main contributors to the superior chemoselectivity of Pt NPs. The organically modified silica could act as an efficient solid ligand for tuning the catalytic performance of metal NPs.