Organically coordinated Cu(II) activated peroxymonosulfate for enhanced degradation of emerging contaminants

Copper ion Cu(II) is generally considered ineffective in activating peroxymonosulfate (PMS). However, our study demonstrates that organically coordinated Cu(II), namely, org-Cu(II) with contaminants such as amoxicillin (AMO), ofloxacin (OFX), sulfadiazine (SDZ), and tetracycline (TET) can efficiently activate PMS under neutral conditions, leading to faster degradation of these emerging contaminants. In contrast, organic contaminants that do not coordinate with Cu(II) do not facilitate PMS activation. Unlike traditional PMS-induced advanced oxidation processes (AOPs), our study identifies trivalent Cu(III) as the primary oxidant intermediate, with monovalent Cu(I) serving as its precursor. In addition, basic conditions was found to be beneficial for the degradation of target pollutants in org-Cu(II)/PMS systems. Moreover, this promotion effect extends to realistic wastewater, suggesting promising application prospects. The potential mechanism of the rate-limiting reduction step from Cu(II) to Cu(I) was further investigated. The interaction strength between the lowest unoccupied molecular orbital (LUMO) of the copper complex formed with organic compounds and the highest occupied molecular orbital (HOMO) of PMS influences the energy of the bonding orbitals. Coordination with organic ligands alters the LUMO of Cu(II), facilitating electron transfer from the HOMO of PMS to copper. This process activates PMS, ultimately leading to the production of Cu(I) and Cu(III). These findings deepen our understanding of PMS-induced AOPs for degrading emerging contaminants and underscore the importance of further research into PMS activation by Org-Cu(II).