Dynamic ZrO_x Clusters Enhanced Redox Couple and ─CHO/OH^- Co-Adsorption for Efficient Electrooxidation of...

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⁺/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 ZrO₂ clusters are reduced to lower-valent suboxides (ZrO_x) during the Ni²⁺→Ni³⁺ 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 Ni²⁺/Ni³⁺ 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/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.