Unraveling a Biomass-Derived Multiphase Catalyst for the Dehydrogenative Coupling of Silanes with Alcohols under Aerobic Conditions

Abstract

Herein, a novel silver and chromium nanostructured N-doped carbonaceous material has been synthesized by a biomass-annealing approach using readily available chitosan as a raw material. The resulting catalyst AgCr@CN-800 has been applied for the dehydrogenative coupling reaction of various silanes with different alcohols to obtain the corresponding silyl ethers under aerobic and mild conditions. Besides excellent activity and selectivity, the as-prepared catalyst exhibits good stability and reusability. Characterization by XRD, XPS, ICP-MS, HRTEM, in combination with careful examination of the structure with Cs-corrected HAADF-STEM revealed that catalyst AgCr@CN-800 comprises Ag and CrN aggregated particles, as well as highly dispersed Ag-Nx and Cr-Nx sites embedded in N-doped graphitic structures. A comparative catalytic study using structure-related catalysts in combination with acid-leaching treatments has shown that the most active species are the Ag particles, and that their activity is boosted by the presence of Cr-derived species. By in-situ Raman spectroscopy experiments, it has been found that the dehydrogenative coupling of silanes with alcohols in the presence of catalyst AgCr@CN-800 takes place through an oxygen-assisted mechanism.