Targeted Decomplexation of Metal Complexes for Efficient Metal Recovery by Ozone/Percarbonate

Abstract

Traditional methods cannot efficiently recover Cu from Cu(II)-EDTA wastewater and encounter the formation of secondary contaminants. In this study, an ozone/percarbonate (O₃/SPC) process was proposed to efficiently decomplex Cu(II)-EDTA and simultaneously recover Cu. The results demonstrate that the O₃/SPC process achieves 100% recovery of Cu with the corresponding k_obs value of 0.103 min^-1 compared with the typical ^•OH-based O₃/H₂O₂ process (81.2%, 0.042 min^-1). The carbonate radical anion (CO₃^•-) is generated from the O₃/SPC process and carries out the targeted attack of amino groups of Cu(II)-EDTA for decarboxylation and deamination processes, resulting in successive cleavage of Cu-O and Cu-N bonds. In comparison, the ^•OH-based O₃/H₂O₂ process is predominantly responsible for the breakage of Cu-O bonds via decarboxylation and formic acid removal. Moreover, the released Cu(II) can be transformed into stable copper precipitates by employing an endogenous precipitant (CO₃^2-), accompanied by toxic-free byproducts in the O₃/SPC process. More importantly, the O₃/SPC process exhibits excellent metal recovery in the treatment of real copper electroplating wastewater and other metal-EDTA complexes. This study provides a promising technology and opens a new avenue for the efficient decomplexation of metal-organic complexes with simultaneous recovery of valuable metal resources.

Keywords: Cu recovery; carbonate radical anion; decomplexation; ozone; percarbonate.