Modulating Hydrogen Adsorption by Unconventional p–d Orbital Hybridization over Porous High‐Entropy Alloy Metallene for Efficient Electrosynthesis of Nylon‐6 Precursor

Abstract Renewable electricity driven electrosynthesis of cyclohexanone oxime (C 6 H 11 NO) from cyclohexanone (C 6 H 10 O) and nitrogen oxide (NO x ) is a promising alternative to traditional environment‐unfriendly industrial technologies for green synthesis of C 6 H 11 NO. Precisely controlling the reaction pathway of the C 6 H 10 O/NO x ‐involved electrochemical reductive coupling reaction is crucial for selectively producing C 6 H 11 NO, which is yet still challenging. Herein, we report a porous high‐entropy alloy PdCuAgBiIn metallene (HEA‐PdCuAgBiInene) to boost the electrosynthesis of C 6 H 11 NO from C 6 H 10 O and nitrite, achieving a high Faradaic efficiency (47.6 %) and almost 100 % yield under ambient conditions. In situ Fourier transform infrared spectroscopy and theoretical calculations demonstrate that unconventional orbital hybridization between d‐block metals and p‐block metals could regulate the local electronic structure of active sites and induce electron localization of electron‐rich Pd sites, which tunes the active hydrogen supply, facilitates the generation and enrichment of key intermediates NH 2 OH* and C 6 H 10 O*, and efficiently promotes their C−N coupling to selectively produce C 6 H 11 NO.