Synergistic activation of persulfate by FeS@SBA-15 for imidacloprid degradation: Efficiencies, activation mechanism and degradation pathways.

Abstract

In this work, FeS supported SBA-15 mesoporous silica catalyst (FeS@SBA-15) was synthesized successfully, characterized and first applied to persulfate (PS) activation for the degradation of imidacloprid in wastewater. The as-prepared 3.5-FeS@SBA-15 presented an impressive imidacloprid removal efficiency of 93.1% and reaction stoichiometric efficiency (RSE) of 1.82% after 5 min, ascribed to the synergetic effects of improved FeS dispersion and abundant surface sites by SBA-15. Electron paramagnetic resonance spectra and quenching experiments proved that both SO4·- and ·OH were produced in FeS@SBA-15/PS system, and SO4·- played a dominant role in the degradation process. The S2- can accelerate the cycling of Fe(III)/Fe(II) during activation and increase the steady-state concentration of Fe(II). More importantly, the constructed heterogeneous system exhibited an efficient and stable catalytic activity over a wide range of pH (3.0-9.0), temperature (283K-313K), inorganic ion (NO3-) and humic acid (1-20 mg/L). Moreover, the density functional theory calculations were conducted to predict the potential reaction sites of imidacloprid. Based on eighteen identified intermediates, four main degradation pathways were proposed: hydroxylation, dechlorination, hydrolysis, and the ring cleavage of the imidazolidine. ECOSAR analysis indicated hydroxylation and dechlorination played a key role in the detoxification of the formed compounds. These findings would provide new insights into the application of FeS@SBA-15 catalyst in wastewater treatment and the removal mechanism of imidacloprid from wastewater.