Synergistic Integration of Pulsed Electrolysis With Bi‐Modified Pd‐Based Electrocatalysts for Efficient Co‐Production of Lactic Acid and Hydrogen

ABSTRACT Coupling value‐added organic oxidation with hydrogen evolution offers a compelling pathway to reduce the energy cost of green hydrogen production while enabling sustainable electrosynthesis. Herein, we report a synergistic strategy that integrates intrinsic electronic structure modulation with extrinsic pulsed electrolysis. A Bi‐modification Pd‐based electrocatalyst supported on iron foam (PdBi/IF) enables highly selective electrooxidation of 1,2‐propylene glycol to lactic acid, achieving Faradaic efficiencies up to 95%. Mechanistic studies reveal that Bi incorporation induces a downward shift of the Pd d ‐band center, resulting in optimized adsorption–desorption behavior of key intermediates. Besides, pulsed electrolysis dynamically regulates the electrode–electrolyte interface, promotes the removal of poisoning intermediates and suppresses lactic acid overoxidation. A synergistic strategy combining electronic modification with pulsed electrolysis is developed to prevent catalyst deactivation during electrooxidation of polyols to lactic acid, while enabling energy‐saving coproduction of hydrogen. This offers a feasible route toward integrated processes that couple high‐value chemical synthesis with energy‐efficient hydrogen generation.