Innovating nanocatalysts with both high intrinsic catalytic activity and high selectivity is crucial for multi-electron reactions, however, their low mass/electron transport at industrial-level currents is often overlooked, which usually leads to low comprehensive performance at the device level. Herein, a Cl-/O2 etching-assisted self-assembly strategy is reported for synthesizing a self-assembled gap-rich PdMn nanofibers with high mass/electron transport highway for greatly enhancing the electrocatalytic reforming of waste plastics at industrial-level currents. The self-assembled PdMn nanofiber shows excellent catalytic activity in upcycling waste plastics into glycolic acid, with a high current density of 223 mA cm-2@0.75 V (vs RHE), high selectivity (95.6%), and Faraday efficiency (94.3%) to glycolic acid in a flow electrolyzer. Density functional theory calculation, X-ray absorption spectroscopy combined with in situ electrochemical Fourier transform infrared spectroscopy reveals that the introduction of highly oxophilic Mn induces a downshift of the d-band center of Pd, which optimizes the adsorption energy of the reaction intermediates on PdMn surface, thereby facilitating the desorption of glycolic acid as a high-value product. Computational fluid dynamics simulations confirm that the gap-rich nanofiber structure is conducive for mass transfer to deliver an industrial-level current.
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