Dynamic ZrOx 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 M2+/Mδ+(δ≥ 3) cycling. Herein, we report a novel ZrOx─MOOH interfacial synergy in electrocatalytic reaction, achieved by modifying traditional MOOH materials with ZrOx as a dynamic electronic regulator for efficient oxidation of alcohols and aldehydes. The ZrO2 clusters are reduced to lower-valent suboxides (ZrOx) during the Ni2+→Ni3+ process. The formed ZrOx 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 Ni2+/Ni3+ redox by modulating the charge density on Ni. The ZrOx─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/cm2, 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.