Water flow-driven electrocatalytic system coupling redox processes for the deep mineralization of halogenated organic...

Electrocatalytic redox processes offer a promising strategy for mineralization of halogenated organic compounds (HOCs), yet remain constrained by sluggish interfacial mass transfer and limited catalytic efficiency due to spatially decoupled reduction-oxidation sites. Herein, we develop a water flow-driven electrocatalytic system (WFD-EC), employing a hydroxyl‑functionalized covalent triazine framework decorated with atomically dispersed Pd sites (Pd₁/BA(OH)-CTF) as the cathodic catalyst. Compared to the static configuration, the WFD-EC exhibits over a 7.78-fold enhancement in florfenicol (FLO) degradation rate (2.247 s^-1) and 83.9 % total organic carbon removal, with substantially reduced energy consumption (EE/O = 3.34 kWh·m^-3·order^-1). In situ Raman spectroscopy and COMSOL simulations reveal that flow-driven convection compresses the Nernst diffusion layer and facilitates interfacial O₂ accumulation, while Pd-N/O co-coordination modulates the electronic environment of Pd sites to enhance Pd-O₂ orbital hybridization and reactive oxygen species (ROS) generation. Mechanistic investigations identified *H and •OH as the dominant reactive species responsible for C-X bond cleavage and subsequent oxidative mineralization, effectively suppressing the accumulation of toxic intermediates. This work presents a redox-integrated, hydrodynamically optimized electrocatalytic platform with broad applicability for scalable, energy-efficient, and deep degradation of HOCs.