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A Spin Descriptor Map Predicts NiFe <sub>2</sub> O <sub>4</sub> for Efficient Electrosynthesis of Cyclohexanone Oxime

Rong Yang, Jinghui Zhao, Yongmeng Wu, Ying Gao, Bin Zhang

2025Angewandte Chemie International Edition5 citationsDOI

Abstract

Abstract The selective hydrogenation of NO to NH 2 OH governs the performance of cyclohexanone oxime electrosynthesis. However, the spin state transition during the NO‐to‐NH 2 OH process, which is directly related to reaction pathways, has long been ignored. Here, we propose a spin locking mechanism via density functional theory and sure independence screening and sparsifying operator. Magnetic sites with medium spin states stabilize the *NHO intermediate by locking the spin configuration of NO to weaken *NH 2 OH adsorption for high selectivity. The spin magnetic moment ( µ S ), the angle between *N–O and the catalyst ( θ ), and the charge state ( q ) are key factors, providing a screening range of the predictive metrics ( µ S · θ ) 3 and (cos θ / q ). The theoretically selected NiFe 2 O 4 delivers 70% Faradaic efficiency for cyclohexanone oxime, and weakened *NH 2 OH adsorption is revealed by in situ spectroscopy. This work highlights the importance of spin regulation in adjusting the selectivity of electrosynthesis.

Topics & Concepts

Spin (aerodynamics)SelectivityCatalysisAdsorptionChemistryDensity functional theoryCyclohexanoneMaterials scienceSpin statesMagnetic momentRange (aeronautics)Cyclohexanone oximeElectrosynthesisComputational chemistryIndependence (probability theory)Physical chemistryWork (physics)OximeTransition metalYield (engineering)Condensed matter physicsMoment (physics)Inorganic chemistryState (computer science)ChemisorptionHeterogeneous catalysisElectrocatalysts for Energy ConversionElectrochemical Analysis and ApplicationsAdvancements in Battery Materials
A Spin Descriptor Map Predicts NiFe <sub>2</sub> O <sub>4</sub> for Efficient Electrosynthesis of Cyclohexanone Oxime | Litcius