Oxygen doping regulation of Co single atom catalysts for electro-Fenton degradation of tetracycline.

CoNOC with CoN (Pd)3 N (Po)1 O1 structure can efficiently catalyse the electro-Fenton reaction to generate –OH to degrade antibiotic pollutants represented by tetracyclines. [Display omitted] • Oxygen-doped Co SACs were prepared using a temperature gradient pyrolysis strategy with nitric acid oxidation method. • DFT calculations explained the excellent catalytic performance was due to the electronic modulation of Co sites by the O doping and N coordination. • TC degradation of 95 % in 120 min and mineralization efficiency of almost 90 % in 180 min were achieved in the electro-Fenton system. • The significant involvement of OH was confirmed, and the degradation pathways of TC have been analyzed and predicted. Electro-Fenton is an effective process for degrading hard-to-degrade organic pollutants, such as tetracycline (TC). However, the degradation efficiency of this process is limited by the activity and stability of the cathode catalyst. Herein, a temperature gradient pyrolysis strategy and oxidation treatment is proposed to modulate the coordination environment to prepare oxygen-doped cobalt monoatomic electrocatalysts (CoNOC). The CoNOC catalysts can achieve the selectivity of 93 % for H 2 O 2 with an electron transfer number close to 2. In the H-cell, the prepared electrocatalysts can achieve more than 100 h of H 2 O 2 production with good stability and the yield of 1.41 mol g catalyst −1 h−1 with an average Faraday efficiency (FE) of more than 88 %. The calculations indicate that the epoxy groups play a crucial role in modulating the oxygen reduction pathway. The O doping and unique N coordination of Co single-atom active sites (CoN (Pd)3 N (Po)1 O1) can effectively weaken the O 2 /OOH* interaction, thereby promoting the production of H 2 O 2. Finally, the electro-Fenton system could achieve a TC degradation rate of 94.9 % for 120 min with a mineralization efficiency of 87.8 % for 180 min, which provides a reliable option for antibiotic treatment. The significant involvement of OH in the electro-Fenton process was confirmed, and the plausible mineralization pathway for TC was proposed. [ABSTRACT FROM AUTHOR]