Electrocatalytic interface reconfiguration enables selective pollutant polymerization.

Electrochemical water treatment is fundamentally bottlenecked by sluggish interfacial mass transfer and diluted reactant concentrations at the electrocatalytic interface. Herein, we report an electric-field-driven interfacial reconfiguration strategy that overcomes these limitations by synergizing an oxygen-functionalized hydrophilic surface with thermal calcination and dynamic electric-field-induced interface reconfiguration. Driven by the synergy of electrophoretic migration (for ionic peroxymonosulfate) and hydrophobic partitioning (for organic pollutants), this reconfigured interface enhances the accessibility and activation of reactants while restructuring interfacial water molecules to overcome the hydration barrier. Mechanistic investigations reveal that applying an electric field (E-CNT/CF-450-PMS) enhances the activation of enriched reactants at the intrinsic vacancy-type defects of CNT/CF-450, increasing the reaction rate constant by a factor of 3.32 relative to the system without an electric field (CNT/CF-450-PMS). Crucially, this strategy induces a paradigm shift from energy-intensive mineralization to energy-efficient controllable oligomerization, effectively lowering the polymerization activation energy by 37.8%. By selectively coupling pollutants into separable, high-molecular-weight aggregates, the system minimizes toxic byproduct formation and achieves a 31.6% reduction in its carbon footprint, as validated by a life cycle assessment. Furthermore, integration into a self-powered microbial fuel cell cathode demonstrates the practical viability of this low-carbon "electrocatalysis-induced polymerization" (EIP) framework. This study provides a fundamental blueprint for overcoming mass-transfer limitations and achieving sustainable water purification.