Sulfur‐Regulated Adaptive Reconstruction of Sn@SnO _x Interfaces via Inducing Buffered Hydroxyl Radical Microenvironment for Enhanced Oxime Electrosynthesis

ABSTRACT

Electrocatalytic oxime synthesis from NO _x and carbonyl compounds offers a sustainable alternative to conventional routes but remains limited by poor *NH ₂ OH control and catalyst instability. Herein, we report a sulfur‐decorated Sn@SnO _x dendritic catalyst for efficient cyclohexanone oxime electrosynthesis from nitrite and cyclohexanone. Under operating conditions, the catalyst undergoes an adaptive reconstruction, where the cathodic potential‐driven sulfur leaching triggers a buffered hydroxyl radical (•OH) microenvironment and suppresses •OH‐mediated SnO _x overgrowth, preserving dynamically stable Sn@SnO _x interfaces. Meanwhile, residual sulfur could modulate the Sn@SnO _x electronic structure, promoting water activation and *H generation to accelerate NO ₂ ⁻ hydrogenation toward the key *NH ₂ OH intermediate for subsequent oximation. At −1.0 V versus reversible hydrogen electrode, the reconstructed catalyst achieves an optimal Faradaic efficiency of 84.4%, with a yield of 87.1% and a yeild rate of 1.48 mmol h ⁻¹  cm ⁻² . This work establishes sulfur‐mediated interfacial regulation as an effective strategy to reconcile activity and durability in Sn‐based catalysts for NO _x ‐to‐oxime conversion.