Core-shell structure dependent reactivity of Fe@Fe₂O₃ nanowires on aerobic degradation of 4-chlorophenol

In this study, core-shell Fe@Fe₂O₃ nanowires with different iron oxide shell thickness were synthesized through tuning water-aging time after the reduction of ferric ions with sodium borohydride without any stirring. We found that these Fe@Fe₂O₃ nanowires exhibited interesting core-shell structure dependent reactivity on the aerobic degradation of 4-chlorophenol. Characterization results revealed that the core-shell structure dependent aerobic oxidative reactivity of Fe@Fe₂O₃ nanowires was arisen from the combined effects of incrassated iron oxide shell and more surface bound ferrous ions on amorphous iron oxide shell formed during the water-aging process. The incrassated iron oxide shell would gradually block the outward electron transfer from iron core for the subsequent two-electron molecular oxygen activation, but more surface bound ferrous ions on iron oxide shell with prolonging aging time could favor the single-electron molecular oxygen activation, which was confirmed by electron spin resonance spectroscopy with spin trap technique. The mineralization of 4-chlorophenol was monitored by total organic carbon measurement and the oxidative degradation intermediates were analyzed by gas chromatography-mass spectrometry. This study provides new physical insight on the molecular oxygen activation mechanism of nanoscale zerovalent iron and its application on aerobic pollutant removal.