Modulating cell stiffness for improved vascularization: leveraging the MIL-53(fe) for improved interaction of titanium implant and endothelial cell.

Vascularization plays a significant role in promoting the expedited process of bone regeneration while also enhancing the stability and viability of artificial bone implants. Although titanium alloy scaffolds were designed to mimic the porous structure of human bone tissues to facilitate vascularization in bone repair, their biological inertness restricted their broader utilization. The unique attribute of Metal-organic framework (MOF) MIL-53(Fe), known as "breathing", can facilitate the efficient adsorption of extracellular matrix proteins and thus provide the possibility for efficient interaction between scaffolds and cell adhesion molecules, which helps improve the bioactivity of the titanium alloy scaffolds. In this study, MIL-53(Fe) was synthesized in situ on the scaffold after hydrothermal treatment. The MIL-53(Fe) endowed the scaffold with superior protein absorption ability and preferable biocompatibility. The scaffolds have been shown to possess favorable osteogenesis and angiogenesis inducibility. It was indicated that MIL-53(Fe) modulated the mechanotransduction process of endothelial cells and induced increased cell stiffness by promoting the adsorption of adhesion-mediating extracellular matrix proteins to the scaffold, such as laminin, fibronectin, and perlecan et al., which contributed to the activation of the endothelial tip cell phenotype at sprouting angiogenesis. Therefore, this study effectively leveraged the intrinsic "breathing" properties of MIL-53 (Fe) to enhance the interaction between titanium alloy scaffolds and vascular endothelial cells, thereby facilitating the vascularization inducibility of the scaffold, particularly during the sprouting angiogenesis phase. This study indicates that MIL-53(Fe) coating represents a promising strategy to facilitate accelerated and sufficient vascularization and uncovers the scaffold-vessel interaction from a biomechanical perspective.

Highly selective detection of adenine and guanine by NH2-MIL-53(Fe)/CS/MXene nanocomposites with excellent electrochemical performance.

Adenine (A) and guanine (G) are mainly found in deoxyribonucleic acid (DNA) and ribonucleic acid (RNA) and play a crucial role in genetic information transfer and protein synthesis. In this study, NH2-MIL-53(Fe)/CS/MXene nanocomposites were prepared for detecting guanine and adenine. With high specific surface area, excellent water dispersion, and numerous active sites, MXene (transition metal carbides, nitrides, and carbonitrides) provides a good platform for loading primitive metal-organic frameworks (MOFs). At the same time, the problem of poor conductivity and dispersion of MOFs is solved. The electrochemical catalytic oxidation of adenine and guanine of NH2-MIL-53 (Fe)/CS/MXene nanocomposites was carried out by differential pulse voltammetry (DPV). Operating voltage of DPV: 0.7-0.9 V (vs. Ag/AgCl) for G, 1.0-1.2 V (vs. Ag/AgCl) for A, 0.8 V (vs. Ag/AgCl), and 1.1 V (vs. Ag/AgCl) for G and A. The concentration ranges for detecting A and G were 3-118 µM and 2-120 µM with detection limits of 0.57 µM and 0.17 µM (S/N = 3), respectively. The nanocomposite was used for detecting G and A in herring sperm DNA, and the content of G and A was found to be about 9 and 11 µM; the RSD values were 3.4 and 1.3%, respectively.

Photocatalytic Aerobic Oxidation of Biomass-Derived 5-HMF to DFF over MIL-53(Fe)/g-C3N4 Composite.

A MIL-53(Fe)/g-C3N4 heterogeneous composite was synthesized and applied in photocatalytic oxidation of 5-hydroxymethylfurfural (5-HMF) to 2,5-diformylfuran (DFF). The systematic investigation indicated that the introduction of MIL-53(Fe) into g-C3N4 increased the specific surface area, broadened the visible-light response region, and promoted the separation efficiency of the photo-generated electron-hole pairs. The 10% MIL-53(Fe)/g-C3N4 heterogeneous composite achieved the best photocatalytic oxidation activity with 74.5% of 5-HMF conversion under simulated sunlight, which was much higher than that of pristine g-C3N4 and MIL-53(Fe). The MIL-53(Fe)/g-C3N4 composite displayed good photocatalytic reusability and stability. Based on the characterization results and photocatalytic performance, a Z-scheme photocatalytic mechanism of the MIL-53(Fe)/g-C3N4 composite was suggested, and a possible reaction route was deduced.

Simplified creation of polyester fabric supported Fe-based MOFs by an industrialized dyeing process: Conditions optimization, photocatalytics activity and polyvinyl alcohol removal.

MIL-53(Fe) was successfully prepared and deposited on the surface carboxylated polyester (PET) fiber by an optimized conventional solvothermal or industrialized high temperature pressure exhaustion (HTPE) process to develop a PET fiber supported MIL-53(Fe) photocatalyst (MIL-Fe@PET) for the degradation of polyvinyl alcohol (PVA) in water under light emitting diode (LED) visible irradiation. On the basis of several characterizations, MIL-Fe@PET was tested for the photocalytic ability and degradation mechanism. It was found that temperature elevation significantly enhanced the formation and deposition of MIL-53(Fe) with better photocatalytic activity. However, higher temperature than 130°C was not in favor of its photocatalytic activity. Increasing the number of surface carboxyl groups of the modified PET fiber could cause a liner improvement in MIL-53(Fe) loading content and photocatalytic ability. High visible irradiation intensity also dramatically increased photocatalytic ability and PVA degradation efficiency of MIL-Fe@PET. Na2S2O8 was used to replace H2O2 as electron acceptor for further promoting PVA degradation in this system. MIL-Fe@PET prepared by HTPE process showed higher MIL-53(Fe) loading content and slightly lower PVA degradation efficiency than that prepared by solvothermal process at the same conditions. These findings provided a practical strategy for the large-scale production of the supported MIL-53(Fe) as a photocatalyst in the future.

Biocompatible Fe-Based Micropore Metal-Organic Frameworks as Sustained-Release Anticancer Drug Carriers.

Sustained-release preparation is a hot spot in antitumor drug research, where the first task is to select suitable drug carriers. Research has revealed that carboxylic acid iron metal⁻organic frameworks (MOFs), constructed from iron (Fe) ions and terephthalic acid, are nontoxic and biocompatible. Due to the breathing effect, the skeleton of this mesoporous material is flexible and can reversibly adapt its pore size through drug adsorption. Therefore, we chose one kind of Fe-MOF, MIL-53(Fe), as a carrier for the anticancer drug oridonin (Ori). In this work, we report the design and synthesis of MIL-53(Fe) and explore its ability as a transport vehicle to deliver Ori. MIL-53(Fe) is characterized by scanning electron microscopy and X-ray powder diffraction. A loading capacity of 56.25 wt % was measured by high performance liquid chromatography. This carrier was safe and nontoxic (cell viability > 95.27%), depending on the results of 3-(4,5-dimethylthiazol-2-yl)--2,5-diphenyltetrazolium bromide assays, lactate dehydrogenase assays, and Annexin V-fluoresce isothiocyanate/propidium iodide double-staining assays. After loading the drug, the structure of the MIL-53(Fe) was not destroyed, and Ori was amorphous in MIL-53(Fe). Based on an analysis of the Ori release profile, results suggest that it lasts for more than seven days in vitro. The cumulative release rate of Ori at the seventh day was about 82.23% and 91.75% in phosphate buffer saline solution at 37 °C under pH 7.2 and pH 5.5, respectively. HepG2 cells were chosen to study the cytotoxicity of Ori@MIL-53(Fe), and the results show that the anticancer ratio of Ori@MIL-53(Fe) system reaches 90.62%. Thus, MIL-53 can be used as a carrier for anticancer drugs and Ori@MIL-53(Fe) is a promising sustained-release drug delivery system for the cancer therapy.

MIL-53(Fe) MOF-mediated catalytic chemiluminescence for sensitive detection of glucose.

Various analytical applications of metal-organic frameworks (MOFs) have been rapidly developed in the past few years. However, the employment of MOFs as catalysts in chemiluminescence (CL) analysis is rare. Here, for the first time, we found that MIL-53(Fe) MOFs could significantly enhance the CL of luminol in the presence of H2O2 in an alkaline medium. The CL intensity in the luminol-H2O2-MIL-53(Fe) system was about 20 times higher than that in the luminol-H2O2 system. Moreover, the XRD pattern of MIL-53(Fe) after CL reaction was almost the same as that of the original MIL-53(Fe), confirming the catalytic role of MIL-53(Fe) in the luminol-H2O2-MIL-53(Fe) system. The possible mechanism behind the enhancing phenomenon was discussed based on the results from the CL spectra, FL probe experiments, and active oxygen species measurements. By coupling with the glucose oxidase-based catalytic oxidation reaction, a sensitive and selective CL method was developed for the detection of glucose. There is a linear relationship between the logarithm of CL intensity and the logarithm of glucose concentration in the range from 0.1 to 10 µM, and a detection limit of 0.05 µM (S/N = 3) is obtained. The proposed method has been applied to the determination of glucose in human serum samples with satisfactory results. Graphical abstract MIL-53(Fe) MOFs are found to greatly enhance the chemiluminescence emission of the luminol-H2O2 system, and this finding resulted in a new chemiluminescence method for biosensing of glucose when coupled with the glucose oxidase.

S-scheme towards interfacial charge transfer between POMs and MOFs for efficient visible-light photocatalytic Cr (VI) reduction.

The establishment of heterojunctions was considered as an exceptional strategy to obtain high-efficiency charge separation and enhanced photocatalytic performance. Herein, a series of FePMo/MIL-53(Fe) (FeM-53) heterojunctions were successfully constructed through in-situ growth of FePMo onto MIL-53(Fe) surface and their photocatalytic capacity were examined by visible-light-induced Cr(VI) reduction. Interestingly, the as-fabricated composites offered various photocatalytic activities controllably relying on the mass ratio of FePMo to MIL-53(Fe). Particularly, the one with the 10% ratio displayed the highest Cr(VI) reduction rate (100%) within 75 min, which was respectively over 4 and 2 folds higher than pure FePMo and MIL-53(Fe). The boosted photoactivity might be ascribed to the establishment of S-scheme heterojunction with suitable band alignment between FePMo and MIL-53(Fe), which broadened the light absorption range and improved charge separation. Further mechanism investigations implied both •O2- and e- were the key reactive species for Cr(VI) removal. Besides, the composite preserved excellent stability after 4 consecutive tests, and performed well in the presence of organic dyes. Such a S-scheme heterojunction may promise for highly efficient environmental mitigation.

Antibody-assisted MIL-53(Fe)/Pt-based electrochemical biosensor for the detection of the nicotine metabolite cotinine.

Antibody-assisted MIL-53(Fe)/Pt was used as an electrochemical biosensor, and a rapid detection method for analysing cotinine content in smokers' saliva was developed based on this sensor. In this sensor, Pt-modified MIL-53(Fe) was modified as an electrode material onto the surface of the working electrode. The amino group was activated with glutaraldehyde and antibodies to cotinine were modified onto the surface and closed with 1% BSA. Cyclic voltammetry (CV), differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) were used to study the electrode assembly and cotinine detection. The DPV results showed an ideal linear relationship between the current value and the logarithm of the concentration. The detection limit was 0.0092 ng/mL. It has good selectivity and cycling stability. The proposed Abs-MIL-53(Fe)/Pt can effectively and sensitively detect cotinine in saliva and has promisingapplications.

Solvothermal In-Situ Synthesis of MIL-53(Fe)@Carbon Felt Photocatalytic Membrane for Rhodamine B Degradation.

In this study, MIL-53(Fe) was innovatively incorporated into carbon felt (CF) by growing in-situ using the solvothermal method. MIL-53(Fe)@carbon felt (MIL-53(Fe)@CF) was prepared and used for the degradation of rhodamine B (RhB). As a new photocatalytic membrane, MIL-53(Fe)@CF photocatalytic membrane has the characteristics of high degradation efficiency and recyclability. Influence of various parameters including MIL-53(Fe)@CF loading, light, electron trapper type, and starting pH on RhB degradation were investigated. The morphology, structure, and degradation properties of MIL-53(Fe)@CF photocatalytic membrane were characterized. Corresponding reaction mechanisms were explored. The results indicated that pH at 4.5 and 1 mmol/L H2O2, 150 mg MIL-53(Fe)@CF could photocatalytically degrade 1 mg/L RhB by 98.8% within 120 min, and the reaction rate constant (k) could reach 0.03635 min-1. The clearance rate of RhB decreased by only 2.8% after three operations. MIL-53(Fe)@CF photocatalytic membrane was found to be stable.

Gasoil removal from aqueous solution using magnetic metal-organic framework adsorbent based on the cellulosic fibrous of Prosopis farcta plant.

Recently, the leakage of Gasoil and other petroleum substances into the seas, surface water, and wastewater has become a global problem; therefore, providing a solution to remove these pollutants seems vital. In the current research, we investigated the removal of floating Gasoil from aqueous solutions. First, the magnetic metal-organic framework was prepared as a new adsorbent based on the cellulosic fibrous of the Prosopis farcta plant (magnetic- cellulose@MIL-53(Fe) carbon aerogel). Using design of experiment, the effect of parameters pH, Gasoil concentration, and adsorbent weight on Gasoil removal were investigated. The adsorbent prepared under optimal parameters can remove 100% floating Gasoil from the aqueous solution. The adsorption capacity of the magnetic- cellulose@MIL-53 (Fe) carbon aerogel is 7.48 g.g-1, which is almost 100 times more than other Fe-based adsorbents. The study of the effect of time showed that the adsorption of Gasoil by the adsorbent is not dependent on time. Gasoil adsorption on magnetic- cellulose@MIL-53(Fe) carbon aerogel follows the Freundlich isotherm with a correlation coefficient of 0.9933. Thermodynamic factors Gibbs free energy, enthalpy, and entropy changes have been calculated. Accordingly, magnetic- cellulose @MIL-53(Fe) carbon aerogel has rapid separation and high stability, and it could be used as a good adsorbent to remove Gasoil from an aqueous solution. With good cycling stability of 86% retention of the initial adsorption value after ten adsorption/desorption cycles.

Cl-based functional group modification MIL-53(Fe) as efficient photocatalysts for degradation of tetracycline hydrochloride.

MIL-53(Fe) catalyst has been widely used to treat the pollutants in water. However, the limited number of electrons in MIL-53(Fe) catalyst has always affected the rate at which Fe3+ can be reduced to Fe2+. We modulated iron-based metal-organic frameworks (MOFs) using organic ligands modified with chlorine functional groups. The characterization results indicate that the 2Cl-MIL-53(Fe) catalyst exhibited the optimal photoelectric properties while maintaining the original structural characteristics. The experimental analyses and the first-principles study suggest that the introduction of a chlorine functional group not only reduced the band gap width and enhanced the visible-light absorption capacity, but also significantly enhanced the electron cloud density of Fe-O clusters. This could further accelerate the redox cycle of Fe(III)/Fe(II), beneficial for H2O2 activation. The constructed Cl-MIL-53(Fe) catalyst exhibited a 3.8 times higher reaction rate constant than pure MIL-53(Fe) catalyst. The specific TCH degradation pathway and mechanism of 2Cl-MIL-53(Fe) treatment are proposed. This study provides a new strategy for iron-based MOFs as a heterogeneous photo-Fenton catalyst to degrade pollutants in water.

Photo-Fenton degradation of carbamazepine and ibuprofen by iron-based metal-organic framework under alkaline condition.

Metal-organic frameworks have been widely used as photocatalytic materials. In this paper, a novel photocatalyst HSO3-MIL-53(Fe) with acidity regulating groups was successfully synthesized by the solvothermal method and applied to remove carbamazepine (CBZ) and ibuprofen (IBP). The photodegradation efficiency of vis/H2O2/HSO3-MIL-53(Fe) can reach 100% when the pH value is 8 or 9. The free radical capture experiment and electron paramagnetic resonance analysis proved that hole (h+), hydroxide radical (·OH), singlet oxygen (1O2), and superoxide Radical (·O2-) are the main active species for pollutants degradation. In the vis/H2O2/HSO3-MIL-53(Fe) system, the high pollutant degradation efficiency under alkaline conditions was attributed to two factors: (1) the acidity adjusting group -HSO3 adjusts the pH value of the whole system, which is beneficial to the photo-Fenton process. (2) The photogenerated electrons of HSO3-MIL-53(Fe) can be captured by Fe (III), H2O2 and O2 to accelerate the reduction of Fe (III) and generate ·OH, 1O2, and ·O2-. Besides, H2O2 can also be activated by Fe (II) and Fe (III). The above processes synergistically improved the photocatalytic efficiency. Based on liquid chromatography-mass spectrometry (LC-MS) analysis, the possible degradation pathways of the two pollutants were proposed.

Indium sulfide deposited MIL-53(Fe) microrods: Efficient visible-light-driven photocatalytic reduction of hexavalent chromium.

The ecosystems and human health were seriously threatened by hexavalent chromium (Cr(VI)) in wastewater. In this article, using the idea of the highly matched energy band structure between indium sulfide (In2S3) and MIL-53(Fe), a Type-II heterojunction has been constructed by loading In2S3 on MIL-53(Fe) microrod to overcome the fault like high recombination rates of photogenerated electron-holes of In2S3. The composite with 20:1 mass ratio of In2S3 to MIL-53(Fe) (IM-2) was adopted as an optimal sample for efficient photocatalytic Cr(VI) reduction under visible light. Various characterization techniques were used to verify the characteristics of composites and delved into the structure-effect relationship between this heterojunction and its activity. Results showed that the reaction rate constants of the photoreduction process over IM-2 was ~ 4 and 26 times higher than those of pure In2S3 and MIL-53(Fe), respectively, and the catalyst could maintain superior removal efficiency (88.6%) and steady crystal structure after four cycles. First-principles calculations further illustrated that the heterostructure formed between In2S3 and MIL-53(Fe) could effectively accelerate the separation of photogenerated electrons and holes, thus improving the photocatalytic reduction performance. Moreover, the active species analyses revealed that the superoxide radicals and electrons were mainly involved in the reduction of Cr(VI).

Vertically grown CeO2 and TiO2 nanoparticles over the MIL53Fe MOF as proper band alignments for efficient H2 generation and 2,4-DCP degradation.

The design of highly efficient photoca talysts for clean energy production and environmental remediation are the grand challenges of scientific research. Herein, TiO2@MIL53Fe and CeO2@MIL53Fe composite photocatalysts are synthesized via solvothermal technique. The SEM and TEM micrographs reveal that TiO2 and CeO2 nanoparticles are vertically grown onto the surface of MIL53Fe MOF. Further, HRTEM micrograph confirmed the formation of heterojunction. It has been investigated that the resultant TiO2@MIL53Fe and CeO2@MIL53Fe photocatalysts exhibit remarkably improved visible light activities for H2 production and 2,4-dichlorophenol (2,4-DCP) degradation in comparison to the bare MIL53Fe photocatalyst. The enhanced photoactivities of the fabricated TiO2@MIL53Fe and CeO2@MIL53Fe photocatalysts are attributed to significantly promoted charge separation as confirmed via the surface photo voltage (SPV) and photoluminescence (PL) results. Further, the photocatalysts exhibit high stability and reusability as confirmed via the recyclable tests. This work will promote the design of MOF-based efficient photocatalysts for clean energy production and environment purification.

Boron nitride nanosheets decorated MIL-53(Fe) for efficient synergistic ibuprofen photocatalytic degradation by persulfate activation.

In this study, based on one-step hydrothermal method, boron nitride nanosheets (BNNs) and MIL-53(Fe) composites (BNFe-X) were successfully prepared and the catalytic performance of BNFe-X on persulfate (PS) activation for ibuprofen (IBP) photodegradation was investigated. The introduction of BNNs changed the morphology of MIL-53(Fe) to be a unique prism-like structure and enhanced the degradation efficiency of IBP, which followed the pseudo-first-order rate kinetics. Among the prepared composites, BNFe-3 (3% BNNs) exhibited the highest IBP degradation activity and possessed strong stability after four cycles. Over 99% IBP removal was achieved at the irradiation time of 60 min. The promoted decomposition rate of IBP could be ascribed to be the activation of PS and the enhanced electrons transfer efficiency between BNNs and MIL-53(Fe). The scavenger studies and electron spin-resonance spectroscopy (ESR) demonstrated the generation of SO2-, OH and O2-, and all these radicals had the different contributions in IBP degradation. Based on the LC-MS-MS and TOC results, the possible decomposition pathways of IBP in BNFe-3/PS system were proposed. This work suggested that the BNNs/Fe-based MOFs composites and PS system had great potential in organic pollutants degradation in aqueous solution.

Unique MIL-53(Fe)/PDI Supermolecule Composites: Z-Scheme Heterojunction and Covalent Bonds for Uprating Photocatalytic Performance.

It is important to find an effective way to enhance the photocatalytic efficiency of metal-organic frameworks. In this work, an organic supermolecule perylene diimide (PDI) semiconductor with a carboxyl terminal was added into the synthesis process of MIL-53(Fe) crystals. The PDI/MIL-53(Fe) (PM) composite photocatalyst was first obtained. The TC-H photodegradation rate of the most efficient 5PM was nearly 94.08% within 30 min, whose apparent reaction rate constant (k) is 4 times that of PDI and 33 times that of MIL-53(Fe), respectively. By investigation and characterization, it has been found that PDI nanofibers were dispersed and fixed in MIL-53(Fe) and bonded to each other by covalent bonds. The radical trap experiments and electron spin resonance analysis illustrated that hydroxyl radical (·OH), superoxide radical (·O2-), and photogenerated holes (h+) were active species. Combined with the band structure of PDI and MIL-53(Fe), it is proposed that the PM photocatalyst was a Z-scheme heterojunction mechanism. Therefore, PM photocatalysts showed excellent charge separation and transfer ability. The performance improvement of 5PM is due to enhanced visible light absorption, efficient charge separation, and excellent redox potential. Five cyclic photocatalytic tests and experiments further demonstrate that the 5PM photocatalyst has a promising future for pollutant removal.

Colorimetric Detection of Salicylic Acid in Aspirin Using MIL-53(Fe) Nanozyme.

The impurity of salicylic acid (SA) in aspirin is a required inspection item for drug quality control. Since free SA is significantly toxic for humans, the content determination of free SA is absolutely necessary to ensure people's health. In this work, a facile colorimetric method was developed for the detection of SA in aspirin by utilizing the MIL-53(Fe) nanozyme. As MIL-53(Fe) possesses enzyme mimicking catalytic activity, 3,3,5,5-tetramethylbenzidine (TMB) can be easily oxidized to blue-oxidized TMB (oxTMB) with the existence of H2O2. Moreover, an inhibition effect on the catalytic activity of the MIL-53(Fe) nanozyme is induced due to the specific complexation between SA and Fe3+ in the center of MIL-53(Fe), which results in a lighter color in the oxTMB. The color change of oxTMB can be seen easily by the naked eye with the addition of different concentrations of SA. Thus, a simple colorimetric platform was established for effectively monitoring SA. A good linear relationship (R 2 = 0.9990) was obtained in the concentration range of 0.4-28 µmol L-1, and the detection limit was 0.26 µmol L-1. In particular, the rationally designed system has been well-applied to the detection of SA impurity in aspirin. Satisfyingly, the detection results are highly in accord with those of HPLC. This novel colorimetric platform broadens the application prospects of nanozymes in the field of pharmaceutical analysis.

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.

A "bottle-around-ship" like method synthesized yolk-shell Ag3PO4@MIL-53(Fe) Z-scheme photocatalysts for enhanced tetracycline removal.

A novel yolk-shell Ag3PO4@MIL-53(Fe) Z-scheme photocatalyst was fabricated via a "bottle-around-ship" like method. Experiments on the treatment of tetracycline upon visible light irradiation showed that the as-prepared photocatalyst possessed excellent photocatalytic performance. Experimental results showed that tetracycline removal efficiency of the yolk-shell Ag3PO4@MIL-53(Fe) Z-scheme photocatalyst was almost 3 times higher than that of MIL-53(Fe). The enhanced photocatalytic performance of Ag3PO4@MIL-53(Fe) nanocomposite could be contributed to its higher surface area, better absorption capability, and greater charge separation efficiency. In addition, the H2O2 concentration detection results for Ag3PO4 (154 µmol/L) and Ag3PO4@MIL-53(Fe) (52 µmol/L) indicated that a big part of generated H2O2 on the Ag3PO4 core would be quickly decomposed by the MIL-53(Fe) shell and generated more reactive species through the photo-Fenton-like reaction, which is beneficial for the improvement of photocatalytic performance. This is a promising approach to fabricate yolk-shell structure photocatalyst and a different aspect to design multiple semiconductor composites heterojunction for environmental remediation.

One-step synthesis of Mn-doped MIL-53(Fe) for synergistically enhanced generation of sulfate radicals towards tetracycline degradation.

Herein, Mn-doped MIL-53(Fe) were fabricated via one-pot solvothermal method and used for peroxymonosulfate (PMS) activation towards tetracycline (TC) degradation from aqueous solution. The characterizations of SEM, FTIR and XRD were utilized to reveal the morphology and structure of the materials. The results showed that Mn-MIL-53(Fe)-0.3 displayed the optimal catalytic performance, the removal efficiency of TC could reach 93.2%. Moreover, the catalytic activity of Mn-MIL-53(Fe) towards TC under different initial pH values, co-existing anions (Cl-,CO32- and SO42-) and humic acid (HA) were investigated. The results of thermodynamic experiment suggested that the catalytic process was endothermic. In addition, integrated with capture experiments results and the characterization results of electron paramagnetic resonance (EPR), which revealed that SO4·- and HO- were the reactive radicals involving in the reaction. More importantly, the possible activation mechanism was discussed in detail based on the X-ray photoelectron spectroscopy results. The active species were generated by the active sites of Fe(II) and Mn(II) on Mn-MIL-53(Fe) effectively activated PMS. Furthermore, the degradation intermediates and possible degradation pathway were investigated by LC-MS. Finally, the catalyst also showed good performance in actual wastewater and demonstrated good recyclability. The Mn-MIL-53(Fe)/PMS system exhibited a promising application prospect for antibiotic-containing waste water treatment.