Interstitial Boron Atoms in Pd Aerogel Selectively Switch the Pathway for Glycolic Acid Synthesis from Waste Plastics

Abstract Electro‐reforming of poly(ethylene terephthalate) (PET) into valuable chemicals is garnering significant attention as it opens a mild avenue for waste resource utilization. However, achieving high activity and selectivity for valuable C2 products during ethylene glycol (EG) oxidation in PET hydrolysate on Pd electrocatalysts remains challenging. The strong interaction between Pd and carbonyl (*CO) intermediates leads to undesirable over‐oxidation and poisoning of Pd sites, which hinders the highly efficient C2 products production. Herein, a nonmetallic alloying strategy is employed to fabricate a Pd‐boron alloy aerogel (PdB), wherein B atoms are induced to regulate the electron structure and surface oxophilicity. This approach allows a remarkable mass activity of 6.71 A mg Pd −1 , glycolic acid (GA) Faradaic efficiency (FE) of 93.8%, and stable 100 h cyclic electrolysis. In situ experiments and density functional theory calculations reveal the contributions of B inserted in Pd lattice on highly effective EG‐to‐GA conversion. Interestingly, the heightened surface oxophilicity and regulated electronic structure by B incorporation weakened *CO intermediates adsorption and enhanced hydroxyl species affinity to accelerate oxidative *OH adspecies formation, thereby synergistically avoiding over‐oxidation and boosting GA synthesis. This work provides valuable insights for the rational design of high‐performance electrocatalysts for GA synthesis via an oxophilic B motifs incorporation strategy.