Title: Discovering the Importance of ClO^• in a Coupled Electrochemical System for the Simultaneous Removal of Carbon and Nitrogen from Secondary Coking Wastewater Effluent

Abstract: Inorganic constituents in real wastewater, such as halides and carbonates/bicarbonates, may have negative effects on the performance of electrochemical systems because of their capability of quenching HO^•. However, we discovered that the presence of Cl– and HCO₃– in an electrochemical system is conducive to the formation of ClO^•, which plays an important role in promoting the simultaneous elimination of biorefractory organics and nitrogen in secondary coking wastewater effluent. The 6-h operation of the coupled electrochemical system (an undivided electrolytic cell with a PbO₂/Ti anode and a Cu/Zn cathode) at a current density of 37.5 mA cm^–2 allowed the removal of 87.8% of chemical oxygen demand (COD) and 86.5% of total nitrogen. The electron paramagnetic resonance results suggested the formation of ClO^• in the system, and the probe experiments confirmed the predominance of ClO^•, whose steady-state concentrations (8.08 × 10^–13 M) were 16.4, 26.5, and 1609.5 times those of Cl₂^•– (4.92 × 10^–14 M), HO^• (3.05 × 10^–14 M), and Cl^• (5.02 × 10^–16 M), respectively. The rate constant of COD removal and the Faradaic efficiency of anodic oxidation obtained with Cl^– and HCO₃^– was linearly proportional to the natural logarithm of the ClO^• concentration, and the specific energy consumption was inversely correlated to it, demonstrating the crucial role of ClO^• in pollutant removal.