Regeneration of Active Sites and Interfacial Environment for Boosting Selective Glycerol Electrooxidation

Abstract

Electrocatalytic oxidation of glycerol to glycerate (GLA) is challenged by catalyst deactivation and product over‐oxidation. Here, we deconvolute the deactivation into two distinct types: chemical (surface oxide accumulation and electrostatic retention of glycerate) and physical (local product enrichment). To address both, we develop a PdCuBi trimetallic metallene (PdCuBiene) that resists chemical deactivation, and combine it with pulsed electrolysis to achieve dual regeneration. Cathodic pulses achieve chemical regeneration by reducing surface oxides and promoting GLA desorption. High flow rates provide physical regeneration by convectively removing accumulated products from the interface. Consequently, GLA selectivity jumps from 68.13% to 85.15% under optimized pulse conditions. In a membrane electrode assembly (MEA) flow electrolyzer, increasing the flow rate from 5 to 60 mL min −1 raises GLA selectivity from 14.28% to 84.18% and sustains operation for 144 h. This dual regeneration concept restores active sites and cleans the interface, offering a broadly applicable strategy for biomass electrooxidation.