Facilitating Proton Coupled Electron Transfer Reaction through the Interfacial Micro Electric Field with Fe─N₄─C in FeMOFs Glass

Abstract The proton‐coupled electron transfer(PCET) reaction plays a crucial role in the chemical transformation process andhas become one of the most concerned elementary reactions. However, the complex kinetics of PCET reaction, which requires the simultaneous transfer of protons and electrons, leads to the dilemma that thermodynamics and kinetics cannot bebalanced and restricts its further development. In this, an interface micro‐electric field (IMEF) basedon Fe─N₄ in FeMOFs (Fe‐Based Metal–Organic Frameworks) glass is designed tosynchronize proton/electron interface behavior for the first time to realizeefficient PCET reaction and optimize reaction thermodynamics and kinetics. The IMEF facilitates the separation of photogenerated electrons and holes, and accelerates Fe(III)/Fe(II) cycle. Driven by near‐surface electric field force, the protons near surfacemigrate to Fe sites and participate in Fe(IV)═O formation and reaction, lowering the reaction energy barrier. Based on the interface regulation ofIMEF, a high‐efficiency PCET reaction is realized, and kinetic reactionrate constant of photocatalytic oxidation of emerging contaminants is increasedby 3.7 times. This study highlights a strategy for IMEFs to modulate PEC Treactions for a wide range of potential applications, including environmental and ecological applications.