Unveiling different antibiotic degradation mechanisms on dual reaction center catalysts with nitrogen vacancies via peroxymonosulfate activation.

Metal-nitrogen-site catalysts are widely recognized as effective heterogeneous catalysts in peroxymonosulfate (PMS)-based advanced oxidation processes. However, the selective oxidation mechanism for organic pollutants is still contradictory. In this work, manganese-nitrogen active centers and tunable nitrogen vacancies were synchronously constructed on graphitic carbon nitride (LMCN) through l-cysteine-assisted thermal polymerization to reveal different antibiotic degradation mechanisms. Benefiting from the synergism of manganese-nitrogen bond and nitrogen vacancies, the LMCN catalyst exhibited excellent catalytic activity for the degradation of tetracycline (TC) and sulfamethoxazole (SMX) antibiotics with first-order kinetic rate constants of 0.136 min and 0.047 min, which were higher than those of other catalysts. Electron transfer dominated TC degradation at low redox potentials, while electron transfer and high-valent manganese (Mn (V)) were responsible for SMX degradation at high redox potentials. Further experimental studies unveiled that the pivotal role of nitrogen vacancies is to promote electron transfer pathway and Mn(V) generation, while nitrogen-coordinated manganese as the primary catalytic active site determines Mn(V) generation. In addition, the antibiotic degradation pathways were proposed and the toxicity of byproducts was analyzed. This work provides an inspiring idea for the controlled generation of reactive oxygen species by targeted activation of PMS.