Coral‐Like Pd ₃ Pb Nanoarchitectures Enable Poisoning‐Resistant Electrosynthesis of Glycolic Acid From PET‐Derived Ethylene Glycol

ABSTRACT Electrochemical upcycling of polyethylene terephthalate (PET) into value‐added chemicals offers a sustainable pathway for mitigating plastic pollution and advancing the global energy transition. However, conventional noble metal catalysts often exhibit severe performance degradation arising from surface oxidation and the accumulation of poisoning intermediates, which ultimately limits catalytic activity and durability. Herein, we employ a rapid microwave‐irradiation strategy to construct coral‐like Pd 3 Pb nanocrystals with a precisely engineered architecture. In situ spectroscopic and kinetic analyses revealed that Pb incorporation disrupts continuous Pd ensembles, thereby suppressing bridged and bidentate adsorption motifs and retarding undesired C─C bond cleavage. Meanwhile, enhanced interfacial * OH availability and electron injection from oxophilic Pb alleviate carbonaceous poisoning and PdO passivation, thereby enabling exceptional long‐term robustness. As a result, Pd 3 Pb achieves a low onset potential (0.28 V vs. RHE), high glycolic acid selectivity (95.2%), and excellent durability (>77 h) in both model electrolytes and real PET hydrolysate. Moreover, a Pd 3 Pb‐based membrane electrode assembly operates stably at 1.0 V at 100 mA cm −2 for 72 h, maintaining an average yield rate of 6.46 mmol h −1 cm −2 . This work elucidates pathways that inhibit catalyst deactivation and informs the rational design of robust catalysts for PET valorization.