Dynamic ZrO x Clusters Enhanced Redox Couple and ─CHO/OH − Co‐Adsorption for Efficient Electrooxidation of Alcohols/Aldehydes

The electrochemical oxidation of biomass‐derived alcohols and aldehydes to produce high‐value carboxylic acids is a more sustainable strategy for achieving biomass upgrading. However, traditional metal oxyhydroxide (MOOH) catalysts suffer from inefficient M 2+ /M δ+ (δ≥ 3) cycling. Herein, we report a novel ZrO x ─MOOH interfacial synergy in electrocatalytic reaction, achieved by modifying traditional MOOH materials with ZrO x as a dynamic electronic regulator for efficient oxidation of alcohols and aldehydes. The ZrO 2 clusters are reduced to lower‐valent suboxides (ZrO x ) during the Ni 2+ →Ni 3+ process. The formed ZrO x enhances the adsorption of the 5‐hydroxymethylfurfural (HMF) (aldehyde C─O) and OH − , and enables faster charge transfer with more NiOOH species participating in the Ni 2+ /Ni 3+ redox by modulating the charge density on Ni. The ZrO x ─NiOOH‐catalyzed HER//HMFOR process achieves stable 2,5‐furandicarboxylic acid (FDCA) yield and Faradaic efficiency (>95%) over 24 consecutive electrolytic cycles. When applied to a flowing HMFOR system (∼1 A/cm 2 , 1.50 V, 200 mM), the overall FDCA yield reaches 90%. Technical‐economic analysis (TEA) demonstrates the economic viability of the system. This work reveals biphasic evolution behavior of catalyst interface, providing a new design paradigm for electrocatalysts in the efficient upgrading of alcohols and aldehydes.