Cu-Co bimetallic organic framework as effective adsorbents for enhanced adsorptive removal of tetracycline antibiotics.

In this study, the removal effect of a new MOF-on MOF adsorbent based on Cu-Co bimetallic organic frameworks on tetracycline antibiotics (TCs) in water system was studied. The adsorbent (Cu-MOF@Co-MOF) were synthesized by solvothermal and self-assembly method at different concentrations of Co2+/Cu2+. The characterization results of SEM, XRD, XPS, FTIR and BET indicated that the MOF-on MOF structure of Cu-MOF@Co-MOF exhibited the best recombination and physicochemical properties when the molar ratio of Co2+: Cu2+ is 5:1. In addition, the Cu-MOF@Co-MOF have a high specific surface area and bimetallic clusters, which can achieve multi-target synergistic adsorption of TCs. Based on above advantages, Cu-MOF@Co-MOF provided a strong affinity and could efficiently adsorb more than 80% of pollutants in just 5 to 15 min using only 10 mg of the adsorbent. The adsorption capacity of tetracycline and doxycycline was 434.78 and 476.19 mg/g, respectively, showing satisfactory adsorption performance. The fitting results of the experimental data were more consistent with the Langmuir isotherm model and pseudo-second-order kinetic model, indicating that the adsorption process of TC and DOX occurred at the homogeneous adsorption site and was mainly controlled by chemisorption. Thermodynamic experiments showed that Cu-MOF@Co-MOF was thermodynamically advantageous for the removal of TCs, and the whole process was spontaneous. The excellent adsorption capacity and rapid adsorption kinetics indicate the prepared MOF-on MOF adsorbent can adsorb TCs economically and quickly, and have satisfactory application prospects for removing TCs in practical environments. The results of the study pave a new way for preparing novel MOFs-based water treatment materials with great potential for efficient removal.

Sustainable removal of tetracycline and paracetamol from water using magnetic activated carbon derived from pine fruit waste.

This work presents highly porous magnetic activated carbon nanoparticles (MPFRC-A) derived from pine fruit residue. The MPFRC-A were produced through a three-step process: physical activation (carbonization temperature: 110-550 °C), chemical activation (H2SO4 (0.1 N, 96%)), and co-precipitation. These nanoparticles were then used to remove tetracycline (TC) and paracetamol (PC) from water. Functionalization with Fe3O4 nanoparticles on the surface of the pine fruit residue-derived activated carbon (PFRC-A) resulted in high saturation magnetization, allowing for separation from aqueous solution using an external magnet. The MPFRC-A adsorbent was characterized by Brunauer-Emmett-Teller (BET) analysis, Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), X-ray diffraction (XRD), and Energy-dispersive X-ray spectroscopy (EDX) analyses, In the experimental section, the effects of various factors on the adsorption process were investigated, including pH, contact time, initial pollutant concentrations, adsorbent dosage, and temperature. Based on these investigations, adsorption isotherm models and kinetics were studied and determined. The results showed that MPFRC-A exhibited a large specific surface area (182.5 m2/g) and a high total pore volume (0.33 cm3/g). The maximum adsorption capacity was achieved at pH 6 and 5 for PC and TC drugs with an adsorbent dose of 400 mg and an initial concentration of 20 mg/L at 25 °C. The study revealed that the experimental data were well-fitted by the Langmuir isotherm model (R2 > 0.98), with maximum uptake capacities of 43.75 mg/g for TC and 41.7 mg/g for PC. Outcomes of the adsorption thermodynamics shows non-spontaneity of the reaction and the adsorption process by all adsorbents was endothermic.

Preparation and Selective Adsorption Performance of the Carboxymethyl Salix psammophila Wood Powder-Imprinted Membrane for Tetracycline.

Carboxymethyl Salix psammophila wood powder-imprinted membranes (CMSM-MIPs) were prepared by using wet spinning technology and molecular-imprinting technology for the selective removal of tetracycline from wastewater. Scanning electron microscopy, X-ray diffraction, thermogravimetry, and X-ray photoelectron spectroscopy characterizations demonstrate that CMSM-MIPs retain the membranous structure of Carboxymethyl Salix psammophila wood powder membranes, successfully encapsulate thin layers of imprinted polymers on the membrane surface, and exhibit excellent thermal stability. The adsorption results showed that CMSM-MIPs had the highest selective adsorption capacity for tetracycline, which was 253.8 mg/g. In addition, the adsorption capacities for oxytetracycline and chlortetracycline were 208.8 and 188 mg/g, respectively. It can be observed that CMSM-MIPs not only exhibit a high adsorption capacity for tetracycline but also demonstrate good adsorption capacities for oxytetracycline and chlortetracycline. The experimental results showed that CMSM-MIPs were best fitted with pseudo-second-order kinetics and most consistent with Freundlich fitting. The regeneration experiment showed that CMSM-MIPs still had good regeneration performance after 5 regeneration cycles. In conclusion, the CMSM-MIPs can not only have the natural adsorption performance of Salix psammophila wood powder but also give it higher selectivity through molecular imprinting, so as to achieve efficient removal of target organic pollutants in water.

A one-stone-two-birds strategy for cellulose dissolution, regeneration, and functionalization as a photocatalytic composite membrane for wastewater purification.

Photocatalytic membranes integrate membrane separation and photocatalysis to deliver an efficient solution for water purification, while the top priority is to exploit simple, efficient, renewable, and low-cost photocatalytic membrane materials. We herein propose a facile one-stone-two-birds strategy to construct a multifunctional regenerated cellulose composite membrane decorated by Prussian blue analogue (ZnPBA) microspheres for wastewater purification. The hypotheses are that: 1) ZnCl2 not only serves as a cellulose solvent for tuning cellulose dissolution and regeneration, but also functions as a precursor for in-situ growth of spherical-like ZnPBA; 2) More homogeneous reactions including coordination and hydrogen bonding among Zn2+, [Fe(CN)6]3- and cellulose chains contribute to a rapid and uniform anchoring of ZnPBA microspheres on the regenerated cellulose fibrils (RCFs). Consequently, the resultant ZnPBA/RCM features a high loading of ZnPBA (65.3 wt%) and exhibits excellent treatment efficiency and reusability in terms of photocatalytic degradation of tetracycline (TC) (90.3 % removal efficiency and 54.3 % of mineralization), oil-water separation efficiency (>97.8 % for varying oils) and antibacterial performance (99.4 % for E. coli and 99.2 % for S. aureus). This work paves a simple and useful way for exploiting cellulose-based functional materials for efficient wastewater purification.

Bacterial cellulose microfilament biochar-architectured chitosan/polyethyleneimine beads for enhanced tetracycline and metronidazole adsorption.

This study investigates the potential applications of incorporating 2D bacterial cellulose microfibers (BCM) biochar into chitosan/polyethyleneimine beads as a semi-natural sorbent for the efficient removal of tetracycline (TET) and metronidazole (MET) antibiotics. Batch adsorption experiments and characterization techniques evaluate removal performance and synthesized adsorbent properties. The adsorbent eliminated 99.13 % and 90 % of TET and MET at a 10 mg.L-1 concentration with optimal pH values of 8 and 6, respectively, for 90 min. Under optimum conditions and a 400 mg.L-1 concentration, MET and TET have possessed the maximum adsorption capacities of 691.325 and 960.778 mg.g-1, respectively. According to the isothermal analysis, the adsorption of TET fundamentally follows the Temkin (R2 = 0.997), Redlich-Peterson (R2 = 0.996), and Langmuir (R2 = 0.996) models. In contrast, the MET adsorption can be described by the Langmuir (R2 = 0.997), and Toth (R2 = 0.991) models. The pseudo-second-order (R2 = 0.998, 0.992) and Avrami (R2 = 0.999, 0.999) kinetic models were well-fitted with the kinetic results for MET and TET respectively. Diffusion models recommend that pore, liquid-film, and intraparticle diffusion govern the rate of the adsorption process. The developed semi-natural sorbent demonstrated exceptional adsorption capacity over eleven cycles due to its porous bead structure, making it a potential candidate for wastewater remediation.

A sustainable carbon aerogel from waste paper with exceptional performance for antibiotics removal from water.

In this work, a sustainable 3D carbon aerogel (AO-WPC) is prepared from waste paper (WP), and used for efficient antibiotics removal from water. The AO-WPC aerogel shows good mechanical property and can recover after 100th of 30 % compression strain. The specific surface area of AO-WPC aerogel is up to 654.58 m2/g. More importantly, this aerogel reveals proper pore size distribution, including micro sized macropores between carbon fibers and intrinsic nano scale mesopores (11.86 nm), which is conducive to remove antibiotics from water. Taking tetracycline (Tc) as an example, the maximum adsorption capacity and adsorption rate of AO-WPC for Tc are as high as 384.6 mg/g and 0.510 g/(mg‧min), respectively, which exhibits significant advantages over most of the recent absorbents, and the adsorption toward Tc reveals good resistance to various environmental factors, including pH, various ions, and dissolved organic matter (DOM). Moreover, good thermal stability enables the AO-WPC aerogel to be regenerated through simple burning, and the adsorption capacity of Tc only decreases by 10.4 % after 10 cycles. Mechanism research shows that hydrogen bonding and π-π electron-donor-acceptor (EDA) interaction play the important role in the adsorption. The excellent mechanical property and adsorption performance imply good practical prospect of the AO-WPC aerogel.

Covalent organic framework aerogel for high-performance solid-phase extraction of tetracycline antibiotics: Experiment and simulated calculation on adsorption behavior.

Three-dimensional sponge-architecture covalent organic frameworks (COFs)-aerogel was successfully designed and synthesized via a freeze-drying template approach, and utilized as an efficient sorbent in solid-phase extraction (SPE). A method for selective enrichment of pharmaceutical contaminants including tetracycline, chlortetracycline, methacycline and oxytetracycline in the environment and food samples was proposed by combining with high performance liquid chromatography (HPLC). To understand the adsorption mechanism, selectivity test and molecular dynamics (MD) simulated calculation were both carried out. The experimental and in-silico results demonstrated that the COFs-aerogel possessed high selectivity for contaminants with H bond acceptors/donors and good efficiency with maximum adsorption capacity up to 294.1 mg/g. The SPE-based HPLC method worked well in the range of 8-1000 ng/mL, with the need of little dose of adsorbent and sample volume while no need of spectrometer, outgoing the reported adsorbents. Under the optimized conditions, the intra-day and inter-day relative standard deviations (RSD) of repeatability were within 2.78-6.29 % and 2.44-8.42 % (n = 5). The results meet the current detection requirement for practical applications, and could be extended for further design of promising adsorbents.

Using lanthanide ions as magnetic and sensing probes for the detection of tetracycline from complex samples.

Tetracycline (TC) is a broad-spectrum antibiotic and has been added to animal feeds to grow livestock under healthy conditions, making it important to have effective methods for rapidly detecting TC in complex samples. In this study, a novel method that uses lanthanide ions (i.e. Eu3+ and Gd3+) as magnetic and sensing probes for the detection of TC from aqueous samples is explored. When dissolving Gd3+ in tris(hydroxymethyl)aminomethane (Tris) buffer at pH 9, magnetic Gd3+-Tris conjugates can be readily generated. The magnetic Gd3+-Tris conjugates possess trapping capacity toward TC from sample solutions via the chelation of Gd3+ and TC. Eu3+ is used as the fluorescence sensing probe against TC on the Gd3+-TC conjugates via the antenna effect. The fluorescence response derived from Eu3+ is increased with the increase of TC trapped on the Gd3+-based probes. The linear dynamic range against TC ranges from 20 to 320 nM, whereas the limit of detection toward TC is ~2 nM. Furthermore, the developed sensing method can be employed for the visual assay of TC with a concentration above ~0.16 µM under UV light illumination in the dark. Furthermore, we have demonstrated the applicability of the developed method to quantify TC in a chicken broth sample with complex matrix. Our developed method offers several advantages, including high sensitivity and good selectivity, for the detection of TC in complex samples.

Synergistic effect of Cu-nanoparticles and ß-cyclodextrin functionalized reduced graphene oxide nanocomposite on the adsorptive remediation of tetracycline antibiotics.

Pollution by tetracyclines antibiotics has a great potential risk on human and animal health even at trace levels. Copper nanoparticles immobilized-ß-cyclodextrin functionalized reduced graphene oxide (Cu/ß-CD/rGO) were successfully prepared as an efficient extractor of tetracycline (TC), oxytetracycline (OTC) and doxycycline (DC) antibiotics from different environmental water samples. Tetracyclines (TCs) are strongly deposited in the matrix of Cu/ß-CD/rGO nanocomposite via surface complexation with the Cu-nanoparticles besides the formation of inclusion complexes with ß-cyclodextrin and π-π interaction of reduced graphene oxide. The novel nanocomposite was characterized by HRSEM, TEM, TGA, FT-IR, XPS, and XRD. The optimization of variables such as the pH, contact time, ionic strength and TC concentration were successfully analyzed. The maximum adsorption capacity (qm) of Cu/ß-CD/rGO calculated from the Langmuir isotherm was 403.2 mg.g-1 for TC, 476.2 mg.g-1 for OTC and 434.8 mg.g-1 for DC at 298 K. The removal efficiency was decreased by 3.7% after five adsorption-desorption cycles. The Cu/ß-CD/rGO nanocomposite was applied for removing TCs from tap water and the Nile River water samples. The novel nanocomposite demonstrated fast and highly efficient removing performance for different TCs with low levels and large sample volume.

Highly efficient removal of antibiotic from biomedical wastewater using Fenton-like catalyst magnetic pullulan hydrogels.

Magnetic nanoparticles that can be employed as Fenton-like catalysts Fenton-like catalysts are attractive materials for degrading antibiotics. In this study, we facilely prepared novel magnetic pullulan (MP) hydrogels by doping modified magnetic nanoparticles into pullulan matrices, which could enhance catalytic degradation performance and strengthen the stability of resulting hydrogels. This is the first time that MP hydrogels have been fabricated successfully and used as Fenton-like catalysts for tetracycline hydrochloride (TCH) degradation. MP hydrogels were characterized and their catalytic TCH degradation abilities were also investigated. The optimized conditions (pH value, Fe3O4 content, H2O2 content and TCH concentration) for TCH degradation were investigated. The optimized system showed excellent degradation efficiency for TCH. Further, the degradation mechanism was comprehensively studied. Finally, synthesized MP hydrogels showed impressive reusability and stability in the cycle experiment. Thus, our findings would open new possibilities to develop magnetic hydrogels in eliminating antibiotic contaminants.

Environmental application of magnetic cellulose derived from Pennisetum sinese Roxb for efficient tetracycline removal.

Pennisetum sinese Roxb is a kind of forage with high yield and high quality. However, because only the leaves are used as feed, most straw is discarded or burned, causing pollution and resources waste. In this study, a magnetic cellulose adsorbent produced by extracting cellulose from Pennisetum sinese Roxb straw was used to adsorb antibiotic tetracycline (TC) from water and can be easily separated. The physicochemical properties of the obtained cellulose samples were studied. The adsorption process was mediated by multiple mechanisms including intra-particle diffusion, chemical ion exchange, hydrogen bonding, and electrostatic interaction. We determined the optimal pH, contact time, initial TC concentration, and temperature before investigating the effects of humic acid and ionic strength on the adsorption process. Our results demonstrate that the magnetic cellulose is a promising adsorbent for the removal of TC from water and is worth to be studied further to develop real-world implementation strategies.

Novel magnetic Fe3O4/g-C3N4/MoO3 nanocomposites with highly enhanced photocatalytic activities: Visible-light-driven degradation of tetracycline from aqueous environment.

In the present work, a series of magnetically separable Fe3O4/g-C3N4/MoO3 nanocomposite catalysts were prepared. The as-prepared catalysts were characterized by XRD, EDX, TEM, FT-IR, UV-Vis DRS, TGA, PL, BET and VSM. The photocatalytic activity of photocatalytic materials was evaluated by catalytic degradation of tetracycline solution under visible light irradiation. Furthermore, the influences of weight percent of MoO3 and scavengers of the reactive species on the degradation activity were investigated. The results showed that the Fe3O4/g-C3N4/MoO3 (30%) nanocomposites exhibited highest removal ability for TC, 94% TC was removed during the treatment. Photocatalytic activity of Fe3O4/g-C3N4/MoO3 (30%) was about 6.9, 5, and 19.9-fold higher than those of the MoO3, g-C3N4, and Fe3O4/g-C3N4 samples, respectively. The excellent photocatalytic performance was mainly attributed to the Z-scheme structure formed between MoO3 and g-C3N4, which enhanced the efficient separation of the electron-hole and sufficient utilization charge carriers for generating active radials. The highly improved activity was also partially beneficial from the increase in adsorption of the photocatalysts in visible range due to the combinaion of Fe3O4. Superoxide ions (·O2-) was the primary reactive species for the photocatalytic degradation of TC, as degradation rate were decreased to 6% in solution containing benzoquinone (BQ). Data indicate that the novel Fe3O4/g-C3N4/MoO3 was favorable for the degradation of high concentrations of tetracycline in water.

Quantification of Veterinary Antibiotics in Pig and Poultry Feces and Liquid Manure as a Non-Invasive Method to Monitor Antibiotic Usage in Livestock by Liquid Chromatography Mass-Spectrometry.

Antibiotics are active substances frequently used to treat and prevent diseases in animal husbandry, especially in swine and poultry farms. The use of manure as a fertilizer may lead to the dispersion of antibiotic residue into the environment and consequently the development of antibiotic-resistant bacteria. Most pharmaceutical active ingredients are excreted after administration, in some cases up to 90% of the consumed dose can be found in the feces and/or urine as parent compound. Therefore, due to antibiotic metabolism their residues can be easily detected in manure. This article describes a method for simultaneous analysis of ciprofloxacin, chlortetracycline, doxycycline, enrofloxacin, lincomycin, oxytetracycline, tetracycline, tiamulin, trimethoprim and tylosin in feces, liquid manure and digestate. Antibiotics were extracted from the different matrices with McIlvaine-Na2EDTA buffer solution and the extract was purified by the use two techniques: d-SPE and SPE (Strata-X-CW cartridges) and final eluent was analyzed by LC-MS and LC-MS/MS. The European Commission Decision 2002/657/EC was followed to conduct the validation of the method. Recoveries obtained from spiked pig and poultry feces and liquid manures samples ranged from 63% to 93% depending on analytes. The analysis of 70 samples (feces, liquid manure and digestate) revealed that 18 samples were positive for the presence of doxycycline, oxytetracycline, tetracycline, chlortetracycline, enrofloxacin, tiamulin and lincomycin. The results obtained in the presented study demonstrated that animal feces can be used as a non-invasive method detection antibiotic usage in animal production.

The roles of extracellular polymeric substances of Pandoraea sp. XY-2 in the removal of tetracycline.

In this study, the roles of extracellular polymeric substances (EPSs) excreted by Pandoraea sp. XY-2 in the removal of tetracycline (TC) were investigated. In the early stage, TC in the solution was mainly removed by the adsorption of EPSs, which accounted for 20% of TC. Thereafter, large amount of TC was transported into the intracellular and biodegraded. EPSs was extracted and the contents of polyprotein and polysaccharides reached their maximum values (30.84 mg/g and 11.15 mg/g) in the first four days. Fourier transform infrared spectroscopy analysis revealed that hydroxyl, methylidyne, methylene and amide I groups in EPSs participated in the adsorption of TC. Furthermore, three-dimensional excitation-emission matrix fluorescence spectroscopy analysis revealed that TC caused the quenching of EPSs fluorescent groups. The quenching mechanism was attributed to static quenching and protein-like substances in EPSs from Pandoraea sp. XY-2 dominated the TC adsorption process. Bioinformatic analysis of Pandoraea sp. XY-2 genome identified multiple genes involved in exopolysaccharide synthesis and EPSs formation. The insights gained in this study might provide a better understanding about the adsorption process of EPSs in tetracycline-contaminated environment.

Extraction of tetracycline in food samples using biochar microspheres prepared by a Pickering emulsion method.

We report for the first time the use of biochar as a stabilizer for oil-in-water (o/w) Pickering emulsion. The emulsion is subsequently used to prepare tetracycline-imprinted biochar composite microspheres (MIPMs) with tailored sizes and good uniformity. The adsorption properties of tetracycline to the MIPMs were investigated using different adsorption experiments including adsorption kinetic experiment, equilibrium binding experiment, selectivity evaluation and competitive adsorption tests. The MIPMs were used as adsorbent for solid phase extraction (SPE) for the extraction of tetracycline present in drinking water, fish, and chicken samples. Under optimal conditions, the results showed good recovery yield ranging from ~73% to ~95% with a relative standard deviation (RSD) ranging from ~0.3% to ~8.4%, respectively.

Specific adsorption of tetracycline from milk by using biocompatible magnetic molecular imprinting material and evaluation by ECD.

Biocompatible magnetic molecularly imprinted polymers (BMMIPs) were prepared with Zein for the first time, and were used to enrich tetracycline compounds selectively. Innovative combination of BMMIPs and electrochemistry to obtain lower detection line to satisfy industrial detection demands. Using Zein as the crosslinking agent, the polymers were synthesized on the surface of Fe3O4 particles. The scanning electron microscope, transmission electron microscope and X-ray diffraction technologies were used to characterize BMMIPs. Through optimization, BMMIPs attained large adsorption capacity (236.40 mg/g) with fast kinetics (40 min) and followed the Langmuir isotherm and pseudo-second-order kinetic models. BMMIPs had good recognition ability, the selective factors of oxytetracycline, chlortetracycline, doxycycline were 4.78, 4.23, and 3.39, respectively. Excellent linearity was attained in the range of 0.025-500 µg/mL, with low detection limits and low quantitation limits of 0.025 and 0.083 µg/mL. According to our exploring, BMMIPs was ideal materials for enrichment of tetracycline in complex biological samples.

Efficient tetracycline adsorptive removal using tricaprylmethylammonium chloride conjugated chitosan hydrogel beads: Mechanism, kinetic, isotherms and thermodynamic study.

In the present study, novel ionic liquid-impregnated chitosan hydrogel beads (CS-TCMA) were fabricated via the reaction of tricaprylmethylammonium chloride (TCMA, Aliquat-336) with the chitosan's amino groups. They were used for the fast adsorption of Tetracycline (TC), as a pharmaceutical compound model, from aqueous solution. It was found that the impregnation of TCMA greatly improved the adsorption behaviour of chitosan toward TC. The optimum adsorbent was determined to be 3 mg/ L in a wide pH range of 5-11. It was a fast process, with a 90% removal efficiency in <45 min. The adsorption kinetic of TC on the CS-TCMA was well described by the pseudo-first-order model and intra-particle diffusion model. The adsorption also obeyed the Langmuir adsorption isotherm model and the maximum adsorption capacity obtained was 22.42 mg/g at 45 °C. The thermodynamic study also revealed the endothermic nature of the process. The adsorption mechanism was also studied.

Glucose enhanced the oxidation performance of iron-manganese binary oxides: Structure and mechanism of removing tetracycline.

In this work, iron-manganese binary oxides (FMO) modified with different proportions of glucose addition (FMOCx) by co-precipitation method showed good activity in activating hydrogen peroxide (H2O2) for tetracycline degradation. The structure and surface characterizations of the FMO and FMOCx were measured by XRD, FTIR, TEM, BET and XPS. With increased glucose addition, FMOCx has more surface functional groups such as -OH and -COOH, particle size decreases, surface area gradually increases, and the ratio of high valence iron and manganese also increases. In addition, the glucose might be oxidized by KMnO4 to form amorphous carbon on the catalyst surface. Glucose modified iron-manganese binary oxides FMOC3 (with 0.003 mol glucose added) showed the highest efficiency removal capability for tetracycline up to 85%, which attribute to it has a larger surface area, more surface functional groups and higher surface active Mn(IV) site content. The results also demonstrated that FMOC3 could efficiently activate hydrogen peroxide. This study proves that glucose modified iron-manganese binary oxides (FMOCx) can offered a possibility of degradation of refractory organic pollutants as an environmentally friendly catalyst in the absence of H2O2 or not.

Removal of Tetracycline in Sewage and Dairy Products with High-Stable MOF.

Serious environmental and human health problems caused by the abuse of antibiotics have attracted worldwide concern. Recently, metal-organic frameworks (MOFs) with high porosity have drawn wide attention for their effects in the adsorption and removal of pollutants from complex matrices. Herein, a high-stable metal organic framework (MOF), i.e., ((ZnCl2)3(L)2·DMF)n, where L=1,3,5-tris((pyridin-4-ylthio)methyl)benzene), MOF 1, was applied to adsorb and remove tetracycline from sewage and dairy products. The results showed that MOF 1 exhibited a strong performance in the adsorption of tetracycline. The effects of initial pH values, adsorbent dose, contact time and ionic strength of the adsorption performance of MOF 1 were investigated. The adsorption kinetics best fit the pseudo-second order model, and the adsorption isotherms matched the Langmuir adsorption model well. It was indicated that both chemical adsorption and physical adsorption play an important role in the adsorption process, and the adsorption of tetracycline was homogeneous and occurred on a monolayer on the surface of MOF 1. Additionally, the stability of MOF 1 and the details of the adsorption mechanism were also investigated. Thus, this study provides a new candidate for the application of MOFs-based adsorbents in the removal of antibiotics from sewage and dairy products.

Fabrication of magnetic trimetallic metal-organic frameworks for the rapid removal of tetracycline from water.

The metal-organic framework (MOF-74) series has the most open metal sites. The metal ions have different bonding strengths with the ligand in MOF-74 and the bond of the ligand can be successively broken to obtain highly active heteroparticles by controlling the temperature, which is difficult to achieve using traditional methods. Magnetic NiCo/Fe3O4-MOF-74, which is fabricated using trimetallic NiCoFe-MOF-74 as a precursor, is simple and rational in comparison with the traditional magnetic core and tunable MOF shell hybrid composites that are formed using a step-by-step assembly strategy. After thermal treatment under a specific atmosphere, NiCo/Fe3O4-MOF-74 shows higher stability, strong magnetism and more active metal sites compared to the original MOF. NiCo/Fe3O4-MOF-74 shows excellent enrichment capability for the removal of tetracycline, with a high removal efficiency that reached 94.1% within 5 min, which is much higher than that of NiCoFe-MOF-74. The main interaction between the adsorbent and analyte is most likely attributed to the open metal sites that can form a stable metal-ligand with the antibiotic molecules. Furthermore, the material can be reused five times without considerable loss. The prepared material has potential applications for removing antibiotics with high efficiency at low cost. Therefore, the experiments described in this study provide a route to a broad class of MOF-based materials for detecting organic contaminants.