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.

Wu Q ，Dong C ，Chen M ，Zhang Y ，Cai M ，Chen Y ，Jin M ，Wei Z ... -  《-》

Nitrogen doped bimetallic sludge biochar composite for synergistic persulfate activation: Reactivity, stability and mechanisms.

As a recycling use of waste activated sludge (WAS), we used high-temperature pyrolysis of WAS to support bimetallic Fe-Mn with nitrogen (N) co-doping (FeMn@N-S), a customized composite catalyst that activates peroxysulphate (PS) for the breakdown of tetracycline (TC). First, the performance of TC degradation was evaluated and optimized under different N doping, pH, catalyst dosages, PS dosages, and contaminant concentrations. Activating PS with FeMn@N-S caused the degradation of 91% of the TC in 120 min. Next, characterization of FeMn@N-S by XRD, XPS and FT-IR analysis highlights N doping is beneficial to take shape more active sites and reduces the loss of Fe and Mn during the degradation reaction. As expected, the presence of Fe-Mn bimetallic on the catalyst surface increases the rate of electron transfer, promoting the redox cycle of the catalyst. Other functional groups on the catalyst surface, such as oxygen-containing groups, accelerated the electron transfer during PS activation. Free radical quenching and ESR analysis suggest that the main contributor to TC degradation is surface-bound SO4•-, along with the presence of single linear oxygen (1O2) oxidation pathway. Finally, the FeMn@N-S composite catalyst exhibits excellent pH suitability and reusability, indicating a solid practicality of this catalyst in PS-based removal of antibiotics from wastewater.

Li Z ，Chen H ，Dong C ，Jin C ，Cai M ，Chen Y ，Xie Z ，Xiong X ，Jin M ... -  《-》

Insights into removal of tetracycline by persulfate activation with peanut shell biochar coupled with amorphous Cu-doped FeOOH composite in aqueous solution.

Xu J ，Zhang X ，Sun C ，Wan J ，He H ，Wang F ，Dai Y ，Yang S ，Lin Y ，Zhan X ... -  《-》

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

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.

Chen J ，Yang Z ，Li W ，Yang Y ，Zhu F ，Huo Z ，Zhou Q ... -  《-》

Development of natural attapulgite derived ferromanganese spinel oxides as heterogeneous catalysts for persulfate activation of tetracycline degradation.

Ferromanganese spinel oxides (MnFe2O4, MFO) have been proven effective in activating persulfate for pollutants removal. However, their inherent high surface energy often leads to agglomeration, diminishing active sites and consequently restricting catalytic performance. In this study, using Al-MCM-41 (MCM) mesoporous molecular sieves derived from natural attapulgite as a support, the MFO/MCM composite was synthesized through dispersing MnFe2O4 nanoparticles on MCM carrier by a simple hydrothermal method, which can effectively activate persulfate (PS) to degrade Tetracycline (TC). The addition of Al-MCM-41 can effectively improve the specific surface area and adsorption performance of MnFe2O4, but also reduce the leaching amount of metal ions. The MFO/MCM composite exhibited superior catalytic reactivity towards PS and 84.3% removal efficiency and 64.7% mineralization efficiency of TC (20 mg/L) was achieved in 90 min under optimized conditions of 0.05 mg/L catalyst dosage, 5 mM PS concentration, room temperature and no adjustment of initial pH. The effects of various stoichiometric MFO/MCM ratio, catalyst dosage, PS concentration, initial pH value and co-existing ions on the catalytic performance were investigated in detail. Moreover, the possible reaction mechanism in MFO-MCM/PS system was proposed based on the results of quenching tests, electron paramagnetic resonance (EPR) and XPS analyses. Finally, major degradation intermediates of TC were detected by liquid chromatography mass spectrometry technologies (LC-MS) and four possible degradation pathways were proposed. This study enhances the design approach for developing highly efficient, environmentally friendly and low-cost catalysts for the advanced treatment process of antibiotic wastewater.

Hu Z ，Tang X ，Ma X ，Guo SQ ，Zhen M ，Ning J ，Xu S ，Shen B ... -  《-》