Complexation Enhances Cu(II)-Activated Peroxydisulfate: A Novel Activation Mechanism and Cu(III) Contribution.

While aqueous free Cu(II) ion is known to be ineffective to activate peroxydisulfate (PDS), here we report for the first time that Cu(II) complexes are potentially effective activators for PDS when the coordination involves suitable ligands. Using cefalexin (CFX) as a representative, studies show that the complex of Cu(II) with CFX can efficiently activate PDS to induce rapid degradation of CFX. Transformation products of CFX by PDS/Cu(II) differ substantially from those generated from the typical radical oxidation process, for example, PDS/Ag(I), but quite resemble the products from oxidation of CFX by Cu(III). Complexation with CFX increases the electron density of Cu(II), favoring electron transfer from Cu(II) to PDS to generate radicals and Cu(III). The produced Cu(III), rather than radicals, plays the primary role in the overall CFX degradation and regenerates Cu(II) in a catalytic cycle. This novel activation process can occur for a wide range of contaminants (cephalosporin, penicillin, and tetracycline antibiotics) and ligands when coordinated with Cu(II), and N-containing functional groups (e.g. amines) were found to form effective Cu(II) complexes for PDS activation. The new findings of this study further broaden the knowledge on PDS activation by aqueous Cu(II), and verify the contribution of Cu(III) to contaminant elimination.