Mechanistic Insights Into Atomic Metal‐Ligand Interface for Ethylene Glycol Electrooxidation to Formate via Robust Interfacial Hydrogen‐Bond Network

ABSTRACT Elucidating the dynamic changes in the interfacial microenvironment at the electrode‐electrolyte interface is indispensable to diverse electrocatalysis systems, in which water functions as the dual source of protons and electrons. However, precisely governing the status of water across intricate interfaces, especially in ethylene glycol oxidation reaction (EGOR) to formic acid remains mystery and challenging. Herein, we demonstrate an ethanol amine‐functionalized porous PdMo metallene (PdMo‐ETA) to optimize electrode‐electrolyte interface via a favorable hydrogen‐bond network, and decipher its synergistic modulation mechanism in EGOR. Notably, PdMo‐ETA delivers a 4.29‐fold enhancement in EGOR mass activity compared with PdMo catalysts, and sustained stability. The formate Faradaic efficiency (FE) is up to 97%, significantly higher than that of pure PdMo (56%). Mechanistically, the interfacial hydrogen‐bond network serves as a “charge‐transfer bridge” to facilitate electron redistribution and intermediate stabilization, thereby reducing the reaction energy barrier for the formation of glycolic acid and subsequent C─C bond cleavage in EGOR. This work underscores the pivotal role of hydrogen‐bond engineering at atomic metal‐ligand interfaces and provides a generalizable design principle for high‐performance electrocatalysts in polyol oxidation reactions.