Silica enhanced activation and stability of Fe/Mn decorated sludge biochar composite for tetracycline degradation

In this study, SiO₂-composited biochar decorated with Fe/Mn was prepared by co-pyrolysis method. The degradation performance of the catalyst was evaluated by activating persulfate (PS) to degrade tetracycline (TC). The effects of pH, initial TC concentration, PS concentration, catalyst dosage and coexisting anions on degradation efficiency and kinetics of TC were investigated. Under optimal conditions (TC = 40 mg L^-1, pH = 6.2, PS = 3.0 mM, catalyst = 0.1 g L^-1), the kinetic reaction rate constant could reach 0.0264 min^-1 in Fe₂Mn₁@BC-0.3SiO₂/PS system, which was 12 times higher than that in the BC/PS system (0.00201 min^-1). The electrochemical, X-ray diffractometer (XRD), Fourier transform infrared spectrum (FT-IR) and X-ray photoelectron spectroscopy (XPS) analysis showed that both metal oxides and oxygen-containing functional groups provide more active sites to activate PS. The redox cycle between Fe(II)/Fe(III) and Mn(II)/Mn(III)/Mn(IV) accelerated the electron transfer and sustained the catalytic activation of PS. Radical quenching experiments and electron spin resonance (ESR) measurements confirmed that surface sulfate radical (SO₄^•-) play a key role in TC degradation. Three possible degradation pathways of TC were proposed based on high-performance liquid chromatography coupled with high-resolution mass spectrometry (HPLC-HRMS) analysis, the toxicity of TC and its intermediates was analyzed by bioluminescence inhibition test. In addition to the enhanced catalytic performance, the presence of silica also improved the stability of the catalyst, as confirmed by cyclic experiment and metal ion leaching analysis. The Fe₂Mn₁@BC-0.3SiO₂ catalyst, derived from low-cost metals and bio-waste materials, offer an environmentally friendly option to design and implement heterogenous catalyst system for pollutant removal in water.