The influence of ferrocene anchoring method on the reactivity and stability of SBA-15-based catalysts in the degradation of ciprofloxacin via photo-Fenton process

Abstract

The study is aimed at evaluation of the impact of ferrocene (Fc) anchoring method on the efficiency of its incorporation on the surface of mesoporous silica SBA-15, as well as the reactivity and stability of these hybrid organic–inorganic materials in degradation of ciprofloxacin (CIP) via photocatalytic, Fenton and photo-Fenton processes. For this purpose, Fc was anchored on SBA-15 supports via three different methods: (i) Schiff base formation, (ii) Friedel–Crafts alkylation, and (iii) click reaction (azide–alkyne cycloaddition). The as-prepared materials were characterized by powder X-ray diffraction, nitrogen physisorption, infrared spectroscopy and inductively coupled plasma optical emission spectrometry, as well as UV-visible and X-ray photoelectron spectroscopies. The highest efficiency of Fc anchoring was obtained when applying the Friedel–Crafts alkylation, while the least effective was the Schiff base formation. As concerns the catalysts activity, all materials exhibited negligible reactivity in the photocatalytic process, but were capable of degrading CIP in the presence of H₂O₂ (Fenton process). For all materials, the highest efficiency of CIP removal was observed for the photo-Fenton reaction. When expressed as the activity of a single Fc site, the most reactive were Fc species from the catalyst prepared by the click reaction. All materials, irrespectively of the ferrocene anchoring method, were deactivating over the reaction time because of Fc leaching. The highest stability in three subsequent reaction cycles was observed for the catalyst prepared by the azide–alkyne cycloaddition. Thus, the click reaction was found to be the best method for the preparation of Fc-containing catalysts for CIP degradation.