The development of high catalytic performance heterogeneous catalysts such as peroxymonosulfate (PMS) activators is important for the practical remediation of organic pollution caused by Rhodamine B (RhB). An economical and facile synthesized composite of copper–magnesium oxide and carbon nitride (CM/g-C3N4) was prepared by the sol-gel/high-temperature pyrolysis method to activate PMS for RhB degradation. CM/g-C3N4 exhibited a splendid structure for PMS activation, and the aggregation of copper–magnesium oxide was decreased when it was combined with carbon nitride. The introduction of magnesium oxide and carbon nitride increased the specific surface area and pore volume of CM/g-C3N4, providing more reaction sites. The low usage of CM/g-C3N4 (0.3 g/L) and PMS (1.0 mM) could rapidly degrade 99.88% of 10 mg/L RhB, and the RhB removal efficiency maintained 99.30% after five cycles, showing the superior catalytic performance and reusability of CM/g-C3N4. The synergistic effect of copper and g-C3N4 improved the PMS activation. According to the analyses of EPR and quenching experiments, SO4•−, •OH and O2•− radicals and 1O2 were generated in the activation of PMS, of which SO4•− and 1O2 were important for RhB removal. The toxicity of RhB was alleviated after being degraded by the CM/g-C3N4/PMS system. This study provides an efficient and promising strategy for removing dyes in water due to the hybrid reaction pathways in the CM/g-C3N4/PMS system.
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