Enhanced Degradation of Decabromodiphenyl Ether via Synergetic Assisted Mechanochemical Process with Lithium Cobalt Oxide and Iron

Abstract

The removal of decabromodiphenyl ether (BDE 209), as a typical persistent organic pollutant (POP), is of worldwide concern. Mechanochemical (MC) processes are promising methods to degrade environmental pollutants, most of which use a single grinding reagent. The performance of MC processes with co-milling agents still needs to be further verified. In this study, an efficient MC treatment with combined utilization of lithium cobalt oxide (LiCoO2) and iron (Fe) as co-milling reagents for BDE 209 degradation was investigated. The synchronous action of LiCoO2 and Fe with a LiCoO2/Fe/Br molar ratio of 1.5:1.67:1 and a ball-to-powder ratio of 100:1 led to almost thorough-paced abatement and debromination of BDE 209 within 180 min using a ball milling rotation speed of 600 rpm. The reduction in particle sizes and the destruction of crystal structure in mixture powders with the increase in milling time induced the enhanced degradation of BDE 209, as characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The X-ray photoelectron spectroscopy (XPS) characterization showed that the valence state of Co was converted from Co(III) to Co(II), and Fe(0) was changed to Fe(III) when treated with an MC process. This indicated that the reductive debromination of BDE 209 by Fe and the following oxidative degradation of debrominated products by LiCoO2 were integrated in a concerted way. It proved the removal of BDE 209 via an MC treatment. The full breakage of C-Br and C-O bonds in BDE 209 was confirmed by Fourier transform-infrared spectrometry (FT-IR) spectra, and a possible abatement pathway was also proposed based on the identified intermediate products using gas chromatography–mass spectrometry (GC-MS). These obtained results indicated that a combination of LiCoO2 and Fe as co-milling reagents is promising in the MC treatment of toxic halogenated pollutants like BDE 209.