Synergy of atomic hydrogen reduction and reactive oxygen species oxidation over confined Mn bifunctional site for electrocatalytic deep mineralization.

Traditional reduction or oxidation processes generating one-component free radicals face challenges in deep dechlorination and mineralization of chlorophenols from wastewater. Herein, an efficient electrocatalytic process has been developed, which couples atomic H* reduction with reactive oxidation species (OH and O) oxidation on a bifunctional cathode for 4 -chlorophenol (4 -CP) removal. The N - doped carbon nanotubes encapsulated manganese nanoparticles was fabricated as cathode, which could generate atomic H* , initiating nucleophilic hydrodechlorination in presence of confined MnO sites. Subsequently, electrophilic oxidation by generating mainly O on confined MnC sites and OH on confined MnO sites, facilitating the oxidative processes. Experimental results and theory calculations demonstrated that reductive dechlorination and oxidative mineralization processes could mutually promote each other, resulting in an enhancement factor of 2.90. At pH 7, this process achieved 100 % removal for 4 -CP, 84 % dechlorination, 76 % total organic carbon (TOC) removal and low energy consumption (0.76 kWh g) within 120 min. Notably, TOC for chlorophenols containing Cl substituents at different positions and real lake water containing 4 -CP could be almost completely removed. This research establishes confined non-noble bifunctional active sites that synergistically enhance reductive dechlorination and oxidative degradation processes, holding significant treatment potential for application in deep mineralization of organochlorine from water/wastewater.