Singlet oxygen generation for selective oxidation of emerging pollutants in a flow-by electrochemical system based on...

The decay of free radicals involved in side reactions is one of the challenges faced by electrochemical degradation of organic pollutants. To this end, a non-radical oxidation system was constructed by a natural air diffusion cathode (ADC) and a Ti-based dimensional stable anode coated by RuO₂ (RuO₂-Ti anode) for cathodic hydrogen peroxide activation by anodic chlorine evolution. The ADC fabricated by the carbon black of BP2000 produced a stable concentration of hydrogen peroxide of 339.94 mg L^-1 (current efficiency of 73.4%) without aeration, which was superior to the cathode made by the XC72 carbon black. The flow-by ADC-RuO₂ system consisted of an ADC and a RuO₂-Ti anode showed high selectivity to aniline (AN) compared to benzoate (BA) in a NaCl electrolyte, whose degradation efficiencies were 97.72% and 1.3%, respectively. Rapid degradations of a mixture of emerging pollutants and AN were also observed in the ADC-RuO₂ system, with pseudo-first-order kinetic constants of 0.51, 1.29, 0.89, and 0.99 min^-1 for Bisphenol A (BPA), tetracycline (TC), sulfamethoxazole (SMX) and AN, respectively. Quenching experiments revealed the main reactive oxygen species for the pollutant degradation was singlet oxygen (¹O₂), which was also identified by the electron spin resonance (ESR) analysis. Finally, the steady-stable content of ¹O₂ was quantitatively determined to be 6.25 × 10^-11 M by the method of furfuryl alcohol (FFA) probe. Our findings provide a fast, low energy consumption and well controlled electrochemical oxidation method for selective degradation of organic pollutants. H₂O₂ generated on an air diffusion cathode by naturally diffused O₂, reacts with ClO^- produced from chloride oxidation on the RuO₂-Ti anode to form singlet oxygen (¹O₂). The electrochemical system shows an efficient oxidation to electron-rich emerging pollutants including bisphenol A, tetracycline, sulfamethoxazole and aniline, but a poor performance on the electron-deficient compounds (e.g., benzoate).