Facilitating C‐C Cleavage via Constructing 4f‐2p‐3d Gradient Orbital Coupling for Ethylene Glycol Electro‐Oxidation

ABSTRACT Polyethylene terephthalate (PET) recycling remains a critical challenge due to the inefficiency and high carbon footprint of conventional methods. Electrocatalytic reforming enables the selective oxidation of ethylene glycol (EG), a PET hydrolysis product, into high‐value chemicals such as formate under mild conditions. Here, an Er‐doped CoNi phosphide catalyst is developed, in which the reconstructed catalyst with 4f‐2p‐3d multi‐orbital coupling among Er‐O‐Co/Ni reconstructs the electronic structure and stabilizes high‐valence metal centers. This modulation enhances *OH adsorption, accelerates C─H dehydrogenation, and lowers the C─C bond cleavage barrier. Consequently, the catalyst achieves 200 mA cm −2 at 1.35 V vs. RHE with a formate Faradaic efficiency of 97.83% and outstanding over 100 h stability. In‐situ spectroscopy and DFT analysis identified the C─C bond cleavage of *CH 2 OHCOOH as the rate‐determining step in the EGOR pathway. Techno‐economic analysis further demonstrates a net profit of $498 per ton of recycled PET, highlighting the practical feasibility of this strategy for sustainable plastic upcycling.