Understanding the Doping Effect and Electrolyte Effect in Electrocatalytic Oxidation of Glycerol With Ligand‐Protected Silver Nanoclusters

ABSTRACT The efficient electrocatalytic oxidation of glycerol (GLY) is one of the most promising routes for the valorization of GLY. Doping has emerged as a powerful strategy to tailor the electrocatalytic performance of silver nanoclusters (Ag NCs), yet the effects of doping mode (surface vs. core) and the interface environment (e.g., electrolyte concentration) on the electrocatalytic performance for Ag NCs toward GLY oxidation remain understood. In this work, surface‐doped Ag 4 M 2 (SR) 8 and core‐doped Ag 24 M(SR) 18 (M = Ni, Pd, Pt; SR = SPhMe 2 ) NCs were synthesized for electrocatalytic GLY oxidation. The results revealed a strong dependence of selectivity on doping mode and electrolyte concentration: under low KOH concentration, Pd‐ and Pt‐doped Ag 4 M 2 NCs exhibited 100% selectivity toward oxalic acid (OA), whereas Pd‐ and Pt‐doped Ag 24 M NCs delivered >95% selectivity for formic acid (FA). In contrast, under high KOH concentration, Pd‐ and Pt‐doped Ag 4 M 2 NCs gave rise to >80% FA, while Pd‐ and Pt‐doped Ag 24 M NCs produced >45% FA. Mechanism studies indicated that Ni doping predominantly enhanced catalytic activity via lowering the activation barrier of the initial reaction step (GLY→glyceraldehyde), whereas Pd and Pt doping modulated selectivity through reducing the energy barrier of the selective branch step (glyceric acid→OA, OA→FA). High KOH concentration promoted the oxidation by increasing the electrochemical active surface area and facilitating electron transfer of Ag NCs. This study provides clear guidance for designing high‐performance Ag‐based electrocatalysts for biomass valorization.