Enhanced Fe(III)-mediated Fenton oxidation of atrazine in the presence of functionalized multi-walled carbon nanotubes

In this study we reported that the presence of functionalized multi-walled carbon nanotubes (FCNT-H) would greatly enhance the degradation of atrazine (ATZ), a model contaminant, in the Fe(III)-mediated Fenton-like system. Efficient ATZ degradation (>90%) was achieved within 30 min in the presence of 20 mg.L^-1 FCNT-H, 2.0 mg.L^-1 Fe(III), and 170 mg.L^-1 H₂O₂, whereas negligible ATZ degradation occurred in FCNT-H free system. The structure and surface chemistry of FCNT-H and other CNTs were well characterized. The formed active species were determined based on ESR analysis, and the mass balance of Fe species during the reaction was monitored. In particular, a new method based on ferrozine complexation was proposed to track the formed Fe(II). The results indicated that ATZ was mainly degraded by the generated hydroxyl radical (HO·), and Fe(III)/Fe(II) cycling was still the rate-limiting step. Besides a small fraction of Fe(III) reduced by FCNT-H, a new pathway was revealed for fast reduction of most Fe(III), i.e., reaction of FCNT-H-Fe(III) complexes with H₂O₂. Comparison of different CNTs-mediated Fe(III)/H₂O₂ systems indicated that such enhanced effect of CNTs mainly resulted from the surface carboxyl group instead of hydroxyl and carbonyl group. Combined with X-ray photoelectron spectroscopy (XPS) analysis, the electron density migration from Fe(III) to FCNT-H possibly resulted in the fast reduction of FCNT-H-Fe(III) complexes by H₂O₂. This study enables better understanding the enhanced Fe(III)-mediated Fenton-like reaction in the presence of MWCNTs and thus, will shed new light on how to develop more efficient similar Fenton systems via Fe(III) complexation.