Hydrosilylation on Hydrogen-Terminated Silicon Surfaces using Pt(dvs): From Efficient Grafting of Olefins to Platinum-Coated Silicon Nanoparticles for Catalysis

Hydrosilylation is an effective method for functionalizing the surface of hydrogen terminated Si substrates and Si nanoparticles (H-SiNPs). We report on the efficiency of Pt-catalyzed hydrosilylation using Karstedt’s catalyst on H-SiNPs and H-Si(100) surfaces. In contrast to the well-established catalytic cycle for the hydrosilylation of olefins using tertiary silanes, we observe that the addition of Pt(0) onto H-SiNPs through oxidative addition is irreversible at room temperature. Optimal reaction conditions are reported for effective hydrosilylation of 1-octene. Higher temperature enable hydrosilylation of 1-octene on the surface of H-SiNPs by favoring reductive elimination of the catalyst. Trapping the catalyst at low temperatures opens a route for the synthesis of Pt(II)-loaded SiNPs that can undergo ligand exchange. Pt-on-Si ensembles were analyzed using Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, and atomic force microscopy. Calcination renders Pt-on-Si nanostructures catalytically active towards hydrogenation of phenyl acetylene. These robust Pt nanocatalysts are anchored on SiNPs which enables their facile recovery and reuse through centrifugation or filtration.