Self‐assembled Gap‐Rich PdMn Nanofibers with High Mass/Electron Transport Highways for Electrocatalytic Reforming of Waste Plastics

Abstract 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 − /O 2 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.