Stable Fe3O4 submicrospheres with SiO2 coating for heterogeneous Fenton-like reaction at alkaline condition

Abstract

In the traditional Fenton process, the efficient generation of hydroxyl radical (HO) strongly relies on an acidic circumstance and the iron ions would precipitate and form large amounts of hazardous iron-containing sludge at alkaline pH. To realize stable heterogeneous Fenton-like catalytic degradation at alkaline condition, Fe3O4 submicrospheres with SiO2 coating were successfully synthesized by using water glass as the silica sources via a facile ultrasound assisted method. The as-obtained Fe3O4@SiO2 spheres were further used as catalysts for the Fenton-like degradation of tetracycline hydrochloride (TC). The Fe3O4@SiO2 submicrospheres exhibited superior catalytic activity in higher pH environment (pH value = 11), and the degradation efficiency toward TC was ca. 80% after ten successive runs. The kinetics for the catalytic degradation of TC were agreed well with the second-order kinetic model. The reaction rate constant (k) over the Fe3O4@SiO2 submicrospheres at a pH value of 11 was 7.69 times greater than that at a pH value of 3. Reactive species scavenging experiments revealed that HO and superoxide radical (O2− / HO2−) played a dominant role during the Fenton-like degradation of TC at pH 3 and pH 11, respectively. Possible Fenton-like degradation pathways of TC were proposed through the identification of intermediates using the high performance liquid chromatography coupled with mass spectrometry (HPLC-MS), which involved cleavage of methyl groups, N-dimethyl group, and hydroxy groups, ring-opening reaction, etc. The degradation efficiency of TC was close to 91.5% and total organic carbon (TOC) in solution was eliminated by about 41.4% at the optimized conditions. In a word, with the unique acidic surface properties and abundant Si-OH bonds, the Fe3O4@SiO2 submicrospheres exhibited well dispersion, good catalytic activity, strong alkali resistance and excellent recyclability in an ultrasonic-Fenton-like system.