Pulsed Electrolysis Programs Relay of Adsorption Reconfiguration and OH Transfer for Neutral HMF-to-FDCA on Ru/MnO2

The electrooxidation of 5-hydroxymethylfurfural (HMFOR) to 2,5-furandicarboxylic acid (FDCA) in neutral media avoids HMF degradation and simplifies purification, yet suffers from sluggish kinetics and low FDCA selectivity. While pulsed electrolysis coupled with a sandwich-structured Ru/MnO2 catalyst has achieved exceptional FDCA yield, its mechanistic role remains unclear. Herein, grand-canonical DFT calculations reveal that pulsed voltage drives dynamic catalyst reconstruction between Ru0/MnO2 and Ru0-RuOx/MnO2, establishing a relay of adsorption reconfiguration and *OH transfer: at low potential, Ru0/MnO2 reorients adsorbed *DFF/*FFCA from double-end to single-end adsorption; at high potential, Ru0-RuOx/MnO2 promotes *OH transfer on the aldehyde carbon. This cross-potential relay circumvents the high energy demand of either structure alone. Additionally, at high potential coadsorbed *DFF stabilizes surface *OH and suppresses overoxidation, favoring HMFOR over OER, while low-potential switching lowers *FDCA desorption and mitigates poisoning. These findings elucidate the multifunctional programming role of pulsed electrolysis and guide rational catalyst-potential design.