Enhanced •Cl generation by introducing electrophilic Cu(II) in Co3O4 anode for efficient total nitrogen removal with hydrogen recovery in urine treatment

Abstract

Urine is a nitrogen-containing waste, but can be used as an attractive alternative substrate for H2 recovery. However, conventional urea oxidation reaction is subject to complex six-electron transfer kinetics and requires alkaline conditions. Herein, an efficient method of enhancing •Cl generation by introducing electrophilic Cu(II) into Co3O4 nanowires anode was proposed, which realized the highly efficient TN removal and H2 production in urine treatment under neutral conditions. The key mechanism is that the electrophilic effect of Cu(II) attracts electrons from the oxygen atom, which causes the oxygen atom to further attract electrons from Co(II), reducing the charge density of Co(II). Electrophilic Cu(II) accelerates the difficult conversion step of Co(II) to Co(III), which enhances the generation of •Cl. The generated •Cl efficiently converts urea to N2, while the electron transport promotes H2 production on the CuO@CF nanowires cathode. Results showed that the steady-state concentration of •Cl was increased to about 1.5 times by the Cu(II) introduction. TN removal and H2 production reached 94.7% and 642.1 μmol after 50 min, which was 1.6 times and 1.5 times that of Co3O4 system, respectively. It was also 2.3 times and 2.1 times of RuO2, and 3.3 times and 2.5 times of Pt, respectively. Moreover, TN removal was 11.0 times higher than that of without •Cl mediation, and H2 production was 4.3 times higher. More importantly, excellent TN removal and H2 production were also observed in the actual urine treatment. This work provides a practical possibility for efficient total nitrogen removal and hydrogen recovery in urine wastewater treatment.