Metal‐Oxide Heterostructure on Hierarchical Nanoporous Alloy for Highly Efficient Ethylene Glycol Electrooxidation Toward Sustainable PET Upcycling

ABSTRACT Renewable electricity‐driven polyethylene terephthalate (PET) hydrolysate electrolysis is a sustainable plastic upcycling technique to produce valuable chemicals, but it usually undergoes insufficient efficiency and selectivity to complicate product separation processes. Here we report nonprecious Co 3 O 4 ‐CuO heterostructure in‐situ integrated on CuCo alloy skeleton as an efficient electrocatalyst to selectively mediate electrooxidation of ethylene glycol in PET hydrolysate to formate and hydrogen for simple and cost‐effective monomer separation. It exhibits exceptional activity (∼930 mA cm −2 at 1.5 V vs. reversible hydrogen electrode) and selectivity (>98 %) as a result of the construction of Co─O─Cu linked CoOOH─CuO multiple active regions for *OH and *OHCH 2 CH 2 OH co‐adsorption, which enables the formation of interfacial hydrogen‐bond coordination to accelerate C─H and C─C bond cleavage. This electrocatalyst is successfully applied in PET hydrolysate electrolyser for stable operation at ∼500 mA cm −2 over 1000 h to continuously produce formate and green hydrogen without performance degradation, showing an industrial perspective of plastic upcycling.