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

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.