Visible light enhanced persulfate activation for degradation of tetracycline via boosting adsorption of persulfate by ligand-deficient MIL-101(Fe) icosahedron.

In this work, Fe-based metal-organic frameworks (Fe-MOFs) are prepared by a simple solvothermal method, in which acetic acid/N, N-dimethylformamide (HAc/DMF) mixture solvents are employed to regulate the particle morphology, exposed facets and ligand defects. At HAc/DMF = 0/50, 5/45 and 8/42 (volume ratio), the irregular particles (MIL-53(Fe)), elongated icosahedrons (5H-MIL-101(Fe)) and icosahedrons (8H-MIL-101(Fe)) are obtained, respectively. Under visible light irradiation (λ > 420 nm) and the addition of sodium persulfate (PS), 5H-MIL-101(Fe) shows the highest degradation activity for tetracycline (TC). Specifically, 80% of TC has been removed by 5H-MIL-101(Fe) within 25 min, and the degradation kinetics rate is 3.03 times higher than that over MIL-53(Fe). The improvement of catalytic activity is mainly attributed to the active facets exposed and ligand defects of 5H-MIL-101(Fe). Density functional theory (DFT) calculation further confirms that the active facets exposed and ligand defects of 5H-MIL-101(Fe) favor the adsorption and activation of PS, benefiting the generation of •SO4-. Besides, a probable degradation pathway of TC is proposed based on trapping experiments and liquid chromatography-mass spectrometry (LC-MS) test. Furthermore, the toxicities of intermediates are predicted by the quantitative structure-activity relationship (QSAR) mathematical model. This work demonstrates that visible light enhanced PS activation (Vis-PSA) can more effectively degrade organic pollutants, and this work also provides a simple strategy to precisely regulate ligand defects and actively exposed facets of Fe-MOFs to enhance the adsorption and activation of PS.

Cheng G ，Yuan C ，Ruan W ，Ma B ，Zhang X ，Yuan X ，Li Z ，Wang D ，Teng F ... -  《-》

Rapid degradation of tetracycline hydrochloride by heterogeneous photocatalysis coupling persulfate oxidation with MIL-53(Fe) under visible light irradiation.

This work demonstrates a facile route to assemble MIL-53(Fe) by solvothermal method. Sulfate radical-based advanced oxidation processes (SR-AOPs) coupling with photocatalysis based on MIL-53(Fe) were investigated under visible light. The catalytic effect of MIL-53(Fe) for the degradation of tetracycline hydrochloride (TC-HCl) was systematically studied, as well as the reusability of the catalyst and the effect of operating parameters. The results indicated that 99.7 % of TC (300 mg/L) could be degraded within 80 min in the SR-AOPs coupling with photocatalysis processes, as compared to 71.4 % for the SR-AOPs and only 17.1 % for the photocatalysis. The trapping experiments and electron spin-resonance spectroscopy (ESR) showed the photogenerated electrons of MIL-53(Fe) under visible light irritation were trapped by persulfate to generated sulfate radicals which effectively suppressed the recombination of photogenerated carriers. And also, the SO4- could be formed by the conversion between Fe (Ⅲ) and Fe (Ⅱ) in MIL-53(Fe). Moreover, OH and O2- generated by the reaction increased significantly due to the increase of SO4- which generated more OH and reduced photogenerated carrier recombination respectively. Thus, the degradation efficiency of TC-HCl was improved. Furthermore, the degradation pathway for TC-HCl was proposed using the theoretical calculations and liquid chromatography coupled with mass spectrometry.

Zhang Y ，Zhou J ，Chen J ，Feng X ，Cai W ... -  《-》

Ibuprofen degradation by a synergism of facet-controlled MIL-88B(Fe) and persulfate under simulated visible light.

The photocatalysis/persulfate (PS) hybrid system has proven to be a promising method for degrading organic pollutants from aqueous solutions. In this study, three MIL-88B(Fe) iron-based metal-organic framework (MOF) phases with different facet content were prepared and used both as photocatalysts and catalysts for PS activation to remove ibuprofen (IBP). The results showed that there was a close correlation between the exposed facets and the catalytic activity. MIL-88B(Fe)-1 (M88B1) with exposed {100} facets and proportionally more {101} facets showed the best catalytic activity. The optimum PS dosage used in this study was 60 mg/L. The presence of Cl-, SO42-, and NO3- all inhibited the degradation of IBP. X-ray photoelectron spectroscopy (XPS) showed that M88B1 possessed more Fe2+ than the other two MIL-88B(Fe) MOF phases, making it easier to generate active radicals through PS activation. The UV-vis diffuse reflectance spectra (DRS), photoluminescence (PL), and electrochemical analysis indicated that M88B1 possessed the highest light absorption, most active sites, and fastest charge transfer ability. Radical scavenging and electron spin resonance (ESR) experiments demonstrated that SO4-•, •OH, O2-•, and 1O2 species participated in the IBP degradation process. Furthermore, density functional theory (DFT) calculations were performed to identify the crystallographic facets, band structure, and total density of states of MIL-88B(Fe) to further confirm the mechanism of MIL-88B(Fe) as a photocatalyst and a PS activator. This work provides new insights into the synergism between photocatalysis and persulfate activation by facet-controlled MOFs for environmental remediation.

Liu N ，Wu J ，Fei F ，Lei J ，Shi W ，Quan G ，Zeng S ，Zhang X ，Tang L ... -  《-》

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 ... -  《-》

A green synthesized recyclable ZnO/MIL-101(Fe) for Rhodamine B dye removal via adsorption and photo-degradation under UV and visible light irradiation.

Amdeha E ，Mohamed RS 《-》