Field‐Effect Induced Interfacial Water Restructuring Accelerates Zinc‐Catalyzed Hydrodeoxygenation

ABSTRACT The deoxygenation of biomass‐derived molecules is thermodynamically challenging yet essential for their conversion to commodity chemicals. Metallic zinc is a promising material for deoxygenation due to its strong reductive properties, but sluggish kinetics and harsh reaction conditions detract from practical application. Here, we hypothesize that zinc‐catalyzed hydrodeoxygenation could be limited by inefficient proton transport due to disordered interfacial water structure. Using the transformation of dihydroxyacetone to acetone as a model reaction, we identified the rate‐determining step to be an Eley–Rideal‐type proton‐coupled electron transfer from water to the hydroxyacetone intermediate. Applying an electric field accelerates this step by restructuring the interfacial hydrogen‐bond network and promoting direct proton transfer, thereby enabling a 10 3 ‐fold increase in surface‐area‐normalized turnover frequency and Faradaic efficiencies of 63%–70% at current densities up to 300 mA/cm 2 . These findings highlight interfacial water restructuring as a powerful lever for enhancing hydrodeoxygenation efficiency.