Assembly of Platinum Nanoparticles and Single-atom Bismuth for Selective Oxidation of Glycerol

Selective oxidation of the secondary hydroxyl group of glycerol to dihydroxyacetone (DHA) is an extremely challenging yet important reaction. The main difficulty is that three hydroxyl groups in glycerol are prone to randomly oxidize, resulting in an unsatisfactory DHA selectivity. We show here that an assembly of platinum nanoparticles (NPs, ~2 nm) and N-stabilized single-atom bismuth (Bi), namely Pt/Bi@NC, shows a record-high DHA selectivity of ~95.0% towards glycerol oxidation under an optimized reaction condition. Characterizations and theoretical calculations verify that single-atom Bi in the vicinity of Pt NPs provides a preferred site to chelate with primary -OH of glycerol, and its secondary -OH is prone to bind surface Pt atom of Pt NP with the shorter Pt-H bond length. This as-formed unique adsorption configuration of glycerol on Pt-Bi dual site significantly facilitates the oxidation of secondary -OH of glycerol, thus contributing to a record-high selectivity to DHA.