Regulating the Potential of Zero Charge to Reconstruct the Electric Double Layer for Boosted Electrocatalytic Plastic Upgrading by Accelerating Mass Transport

ABSTRACT The electrocatalytic oxidation of polyethylene terephthalate (PET)‐derived ethylene glycol (EGOR) to glycolic acid (GA) offers a sustainable approach for plastic valorization and low‐carbon chemical production. Conventional strategies have primarily focused on electronic modulation of catalytic sites to improve intrinsic activity, while neglecting the pivotal influence of the interfacial electric double layer (EDL). Here, we employed oxygen vacancies (OVs)‐rich Pd/MoO _3‐x catalyst to investigate how OVs drive EDL reconstruction and thus promote EGOR. Comprehensive experiments and molecular dynamics simulations revealed that OVs lower the potential of zero charge (PZC) of Pd/MoO _3‐x , which in turn redistributes interfacial cations and reconstructs a spatially accessible, hydrogen‐bond‐connected, and dynamically flexible EDL, thereby promoting reactant migration. By systematically varying the OVs concentration, we establish a PZC–EDL–kinetics relationship in which an optimal PZC maximizes EDL reconstruction and delivers a current density of 1000 mA cm ⁻² at 0.84 V vs RHE, with high FE (95.3%) and GA selectivity (97.1%). This work not only provides new insights into OVs‐mediated interfacial mechanisms in electrocatalytic plastics upgrading but also identifies PZC as an actionable design lever for tailoring the EDL structure and thereby modulating reaction kinetics in low‐potential alkaline electrocatalysis.