Asymmetric p-d-p Orbital Hybridization and Atomically Ordered Configuration in Intermetallic PdInBi Metallene Induced Short-Path Hydrogen Spillover for Electrosynthesis of Oximes

Electrosynthesis of cyclohexanone oxime (CYCO) from nitrite (NO 2 ⁻) and cyclohexanone (CYC) offers a sustainable alternative for green CYCO production. However, precise control of the NO 2 ⁻ reduction pathway to generate *NH 2 OH intermediates while suppressing CYC/CYCO hydrogenation and hydrogen evolution reaction remains challenging. Here, an intermetallic PdInBi metallene ( i -PdInBiene) catalyst was designed for CYCO electrosynthesis, achieving nearly 100% yield and an optimal Faradaic efficiency of 40.73 ± 2.74%. Combination of in situ characterizations with theoretical calculations reveal that the asymmetric p-d-p orbital hybridization in atomic-scale ordered configuration could regulate the local electronic structure of active sites and induce short pathway-hydrogen spillover. The *H modulation over specific active sites favors the selective reduction of NO 2 ⁻ to *NH 2 OH, promotes its spontaneous coupling with CYC to produce CYCO, while suppressing undesired side reactions. The system’s economic feasibility and broad substrate applicability further highlight its potential as a mild, sustainable strategy for oxime electrosynthesis.