Influence of Organic Amino and Thiol Ligands on the Geometric and Electronic Surface Properties of Colloidally Prepared Platinum Nanoparticles

The influence of organic ligands on the geometric and electronic surface properties of colloidally prepared Pt nanoparticles (Pt NPs) was investigated by means of diffuse reflectance infrared spectroscopy (DRIFTS) and using CO as probe molecule. Dodecylamine (DDA) and dodecylthiol (DDT) were used as surface functionalizing ligands that exhibit the same hydrocarbon tail but different functional groups. While for DDA an electronic donor effect as well as a geometric effect was found, the effect of DDT was mainly geometric in nature. For high DDA and DDT coverages, on-top sites were blocked for CO adsorption to a higher extent than bridge and threefold hollow sites. Whereas DDA is only weakly adsorbed and displaced by strongly binding adsorbates (e.g., CO), DDT is strongly attached to the particle surface forming an evenly distributed capping layer. With decreasing thiol coverage, blocking of bridge and threefold hollow sites became more pronounced than on-top site blocking. The influence of both ligands on the selectivity of the hydrogenation of crotonaldehyde catalyzed by Pt NPs was investigated. For amino-functionalized NPs the catalytic properties did not differ from that of "unprotected" Pt NPs. In contrast, an increased selectivity can be found for thiol-functionalized particles, which, according to the IR-spectroscopic investigations, was attributed to a geometric modification of the surface by the ligand.