Charge‐Polarized Interfacial Engineering Enables Radical Management for 1000 h Electrosynthesis of Para‐ Benzoquinone

ABSTRACT Radical‐mediated organic electrosynthesis frequently suffers from limited selectivity and catalytic instability, largely arising from uncontrolled radical coupling and overreaction. These challenges intensify under large‐current conditions, where accelerated radical generation promotes competing side reactions and undermines practical implementation. Here, we introduce a charge‐polarized interfacial engineering strategy to address these issues, demonstrated using a Cr 2 O 3 /Ru‐Fe 2 O 3 heterostructure to drive the selective electro‐oxidation of phenol to para‐ benzoquinone ( p‐ BQ). The polarized interface enforces a vertical adsorption configuration of phenoxy radicals, suppressing Langmuir−Hinshelwood polymerization while stabilizing high‐valent Ru oxidative centers and facilitating rapid desorption of p‐ BQ product. As a result, the catalyst achieves 1000 h of continuous p‐ BQ electrosynthesis at record steady‐state current densities above 40−50 mA cm −2 , delivering high product selectivity and parallel hydrogen production at 1.0 V in an asymmetric hybrid seawater electrolyzer. This work establishes interfacial radical management as an effective framework for efficient electrosynthesis of value‐added chemicals.