Ball-milled zero-valent iron with formic acid for effectively removing Cu (II)-EDTA accomplished by EDTA ligands oxidative degradation and Cu (II) removal

Heavy metal complexes in industrial wastewater are challenging to be removed by conventional methods arising from their stable chelating structure. In this study, zero-valent iron (ZVI) was ball-milled with tiny formic acid (FA), and the as-prepared sample (FA-ZVIbm) was attempted to eliminate a model heavy metal complex of Cu(II)-ethylenediaminetetraacetic acid (Cu(II)-EDTA). The addition of FA to ball-milling could dramatically enhance the performance of ball-milled ZVI (ZVIbm) towards Cu(II)-EDTA removal and increase the removal rate constant by 80 times. This conspicuous improvement of Cu(II)-EDTA elimination was attributed to the ferrous formate (Fe (HCOO)2) shell formed on the surface of FA-ZVIbm. Results revealed that the Fe(HCOO)2 shell facilitated the activation of O2 to reactive oxygen species (ROS) and the leaching of Fe3+. Cu(II)-EDTA was decomplexed through both oxidative destruction and Fe3+ replacement, and the released Cu2+ was reduced by FA-ZVIbm and immobilized synchronously. Meanwhile, the ligands underwent oxidative degradation by ROS, thus avoiding the re-chelation ecological risk. Impressively, FA-ZVIbm could achieve cyclic treatment of actual copper complex wastewater and possessed promising advantage in treatment cost. This study would offer a promising approach for eliminating Cu(II)-EDTA through EDTA ligands degradation and synchronous Cu(II) removal, moreover to shed light on the decomplexation mechanism.

Automated summary

This study developed a sample called FA-ZVIbm by ball-milling zero-valent iron (ZVI) with formic acid (FA), which showed remarkable performance in removing heavy metal complexes, specifically Cu(II)-ethylenediaminetetraacetic acid (Cu(II)-EDTA). The addition of FA greatly enhanced the removal efficiency, increasing the removal rate constant by 80 times. The improvement was attributed to the formation of a ferrous formate (Fe (HCOO)2) shell on the surface of FA-ZVIbm, which facilitated the activation of reactive oxygen species (ROS) and the leaching of Fe3+.