Fe@Fe2O3 core-shell nanowires enhanced Fenton oxidation by accelerating the Fe(III)/Fe(II) cycles

In this study we demonstrate Fe@Fe2O3 core-shell nanowires can improve Fenton oxidation efficiency by two times with rhodamine B as a model pollutant at pH > 4. Active species trapping experiments revealed that the rhodamine B oxidation enhancement was attributed to molecular oxygen activation induced by Fe@Fe2O3 core-shell nanowires. The molecular oxygen activation process could generate superoxide radicals to assist iron core for the reduction of ferric ions to accelerate the Fe(III)/Fe(II) cycles, which favored the H2O2 decomposition to produce more hydroxyl radicals for the rhodamine B oxidation. The combination of Fe@Fe2O3 core shell nanowires and ferrous ions (Fe@Fe2O3/Fe2+) offered a superior Fenton catalyst to decompose H2O2 for producing (OH)-O-center dot. We employed benzoic acid as a probe reagent to check the generation of (OH)-O-center dot and found the (OH)-O-center dot generation rate of Fe@Fe2O3/Fe2+ was 2-4 orders of magnitude larger than those of commonly used iron based Fenton catalysts and 38 times that of Fe2+. The reusability and the stability of Fe@Fe2O3 core shell nanowires were studied. Total organic carbon and ion chromatography analyses revealed the mineralization of rhodamine B and the releasing of nitrate ions. Gas chromatograph-mass spectrometry was used to investigate the degradation intermediates to propose the possible rhodamine B Fenton oxidation pathway in the presence of Fe@Fe2O3 nanowires. This study not only provides a new Fenton oxidation system for pollutant control, but also widen the application of molecular oxygen activation induced by nanoscale zero valent iron. (C) 2014 Elsevier Ltd. All rights reserved.