Adsorption configuration control on Pt-Bi2O3 for the oriented conversion of glycerol to glyceric acid via terminal hydroxyl oxidation

Glycerol, a byproduct of biodiesel production, can be efficiently converted into valuable chemicals through electrocatalytic reaction. In this study, platinum (Pt) nanocrystals decorated on bismuth oxide (Bi 2 O 3 ) nanosheets (PtBi DONS) with an optimal Pt:Bi ratio of 1:1 were successfully synthesized using a galvanic replacement method. Pt 1 Bi 1 DONS exhibit remarkable electrocatalytic performance for glycerol electrooxidation, achieving an excellent catalytic activity (current of 0.82 A mg Pt –1 at 0.67 V vs. reversible hydrogen electrode (RHE)) and an exceptional selectivity of 96.6% for C 3 products, particularly glyceric acid. The superior performance stems from two key factors: (1) electron transfer from Bi 2 O 3 to Pt creates electron-rich Pt sites that suppress C–C bond cleavage and (2) Bi 2 O 3 facilitates favorable glycerol adsorption configurations through multiple hydroxyl group interactions. Mechanistic studies using operando spectroscopy and electrochemical impedance spectroscopy revealed that the synergistic effect between Pt and Bi 2 O 3 promotes rapid charge transfer and stable intermediate formation. Moreover, PtBi DONS showed excellent versatility in oxidizing other polyols compared with monoalcohols.