Robust Formate Electrosynthesis from Mixed Biomass Polyols by a Direct Carbon–Carbon Bond Cleavage Route

Electrocatalytic upcycling of biomass-derived mixed polyols offers an alternative to produce high-value-added chemicals with water as the oxygen source in a sustainable manner. However, the conventional electrocatalytic route involves the stepwise carbon–carbon (C–C) bond cleavage pathway and requires precise engineering of applied potential, which remarkably increases the separation and purification cost and severely restricts further utilization of biomass resources. In this work, we develop, for the first time, a direct C–C bond cleavage route that achieves robust electrosynthesis of high-purity, value-added formate from mixed polyols derived from biomass resources, with a mesoporous cobalt–copper–zinc oxide (named meso-(CoCuZn) 3 O 4 ) electrocatalyst. Without the side reactions that formed multicarbon intermediates, meso-(CoCuZn) 3 O 4 delivered a remarkable performance for efficient formate electrosynthesis, holding a superior Faradaic efficiency of 96.7% and a recordable yield rate of 0.53 mmol cm –2 h –1 with glycerol as the substrate. This route further enables robust electrosynthesis of the formate derivative, higher-valued potassium dimethylate, from biomass-derived mixed polyols, with high cost-effectiveness for biomass upcycling in industrial applications. This work provides guidelines in designing new electrocatalytic pathways for the sustainable electrosynthesis of value-added chemicals from waste biomass resources.