MXene-supported MIL-88A(Fe) as persulfate activator for removal of tetracycline

Abstract

The poor conductivity, poor stability, and agglomeration of iron-based metal organic framework MIL-88A(Fe) limit its application as persulfate (PS) activator in water purification. Herein, MXene-supported MIL-88A(Fe) composites (M88A/MX) were synthesized to enhance its adsorption and catalytic capability for tetracycline (TC) removal. Scanning electron microscope (SEM), X-ray diffractometer (XRD), Fourier transform infrared spectrometer (FT-IR), and X-ray photoelectron spectroscopy (XPS) were used to characterize prepared materials, confirming the successful attachment of MIL-88A(Fe) to the surface of MXene. M88A/MX-0.2 composites, prepared with 0.2 g MXene addition, exhibit optimal degradation efficiency, reaching 98% under conditions of 0.2 g/L M88A/MX-0.2, 1.0 mM PS, 20 ppm TC, and pH 5. The degradation rate constants of M88A/MX-0.2 were 0.03217 min^-1, which was much higher than that of MIL-88A(Fe) (0.00159 min^-1) and MXene (0.00626 min^-1). The removal effects of reaction parameters, such as dosage of M88A/MX-0.2 and PS; initial solution pH; and the presence of the common co-existing constituents (humic acid and the inorganic anions) were investigated in detail. Additionally, the reuse of M88A/MX-0.2 showed that the composites had good cycling stability by recurrent experiments. The results of electron paramagnetic resonance (EPR) and quenching experiments indicated that ·OH, ·SO₄^-, and ·O₂^- were involved in the M88A/MX-0.2/PS system where persulfate oxidation process was activated with prepared M88A/MX-0.2. In addition, the intermediates of photocatalytic degradation were determined by HPLC-MS, and the possible degradation pathways of the target molecules were inferred. This study offered a new avenue for sulfate-based degradation of Fe-based metal organic framework.

Keywords: Free radical production; MIL-88A(Fe); MXene; Persulfate activation; Tetracycline degradation.