Ni‐Induced Low‐Valence Tungsten Oxide for Highly Selective and Stable Glycerol Electro‐Oxidation to Formic Acid

ABSTRACT Electrocatalytic upgrading of renewable biomass‐derived glycerol represents a sustainable method to produce value‐added chemicals, but the complex reaction network of key intermediates during the glycerol oxidation poses challenges to product selectivity. Herein, we report a nickel‐doped tungsten oxide catalyst grown on nickel foam (Ni‐WOx/NF) for the highly selective electrooxidation of glycerol to formic acid (FA). This optimized catalyst achieves an FA Faraday efficiency (FE) of 95.1% and operates stably for over 18 h, outperforming conventional non‐precious metal catalysts. Mechanistic understanding revealed that nickel doping effectively modulates the valence states of tungsten, increasing the proportion of low‐valent W 4+ species. This promotes the desorption of FA from the catalytic interface, thereby inhibiting its over‐oxidation and enhancing selectivity. Taking a step forward, an integrated electrocatalytic system coupling the anodic glycerol oxidation reaction (GOR) with the cathodic nitrate reduction reaction (NO 3 −RR) is constructed. This system enables the simultaneous coproduction of FA and ammonia (NH 3 ), achieving a high FE for FA of 96.9% along with sustained stability over 12 h, demonstrating significant potential for practical applications. This work demonstrates a sustainable catalytic system for selective glycerol oxidation by precisely regulating the reaction pathways of key intermediates.