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

Renewable electricity driven electrosynthesis of cyclohexanone oxime (C6H11NO) from cyclohexanone (C6H10O) and nitrogen oxide (NOx) is a promising alternative to traditional environment‐unfriendly industrial technologies for green synthesis of C6H11NO. Precisely controlling the reaction pathway of the C6H10O/NOx‐involved electrochemical reductive coupling reaction is crucial for selectively producing C6H11NO, which is yet still challenging. Herein, we report a porous high‐entropy alloy PdCuAgBiIn metallene (HEA‐PdCuAgBiInene) to boost the electrosynthesis of C6H11NO from C6H10O 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 NH2OH* and C6H10O*, and efficiently promotes their C−N coupling to selectively produce C6H11NO. A porous high‐entropy alloy PdCuAgBiIn metallene was synthesized and demonstrated high performance for electrosynthesis of cyclohexanone oxime (C6H11NO). Experimental and theoretical studies validated that unconventional p‐d orbital hybridization could tune the local electronic structure of active sites to manipulate active hydrogen supply, which facilitates the generation and enrichment of key intermediates and promotes the formation of C6H11NO.