Selenization governs the intrinsic activity of copper-cobalt complexes for enhanced non-radical Fenton-like oxidation toward organic contaminants

Abstract

Non-radical oxidation pathways in the Fenton-like process have a superior catalytic activity for the selective degradation of organic contaminants under complicated water matrices. Whereas the synthesis of high-performance catalysts and research on reaction mechanisms are unsatisfactory. Herein, it was the first report on copper-cobalt selenide (CuCoSe) that was well-prepared to activate hydrogen peroxide (H₂O₂) for non-radical species generation. The optimized CuCoSe+H₂O₂ system achieved excellent removal of chlortetracycline (CTC) in 10 min at neutral pH along with pleasing reusability and stability. Moreover, it exhibited great anti-interference capacity to inorganic anions and natural organic matters even in actual applications. Multi-surveys verified that singlet oxygen (¹O₂) was the dominant active species in this reaction and electron transfer on the surface-bound of CuCoSe and H₂O₂ likewise played an important role in direct CTC oxidation. Where the synergetic metals of Cu and Co accounted for the active sites, and the introduced Se atoms accelerated the circulation efficiency of Co³⁺/Co²⁺, Cu²⁺/Cu⁺ and Cu²⁺/Co²⁺. Simultaneously, the produced Se/O vacancies further facilitated electron mediation to enhance non-radical behaviors. With the aid of intermediate identification and theoretical calculation, the degradation pathways of CTC were proposed. And the predicted ecotoxicity indicated a decrease in underlying environmental risk.

Keywords: CTC; CoCuSe; Fenton-like; Non-radical degradation; Reaction mechanism.