Metal Organic Framework UiO-66 Research Articles

UiO-66 MOF/Zr-di-terephthalate/cellulose hybrid composite synthesized via sol-gel approach for the efficient removal of methylene blue dye.

This research addresses the issue of organic dye pollution in water by developing eco-friendly, cost-effective adsorbents. Zr-di-terephthalate organic-inorganic hybrid materials, with and without cellulose, were synthesized using a one-pot sol-gel method with zirconium butoxide and terephthalic acid. The materials were characterized by XRD, FTIR, XPS, SEM, EDS, TEM, and BET analysis and showed a crystalline structure with some amorphous content, high surface area, and small pores, indicative of a composite form containing UiO-66 metal-organic frameworks (MOFs). Adsorption studies on methylene blue dye showed that both materials followed Langmuir isotherms, with maximum adsorption capacities of 147.54 mg/g for Zr-(TPA)2-U and 151.38 mg/g for Zr-(TPA)2-UC. The materials exhibited rapid adsorption within a short period of 30 min and adhered to pseudo-second order kinetics. The adsorption process was spontaneous and endothermic, driven by electrostatic interactions, π-π stacking, pore filling, van der Waals forces, and hydrogen bonding. The fact that the composite materials contain the UiO-66 structure contributed to their effective adsorption by increasing the crystalline properties of the material. The hybrids also showed excellent reusability, maintaining high efficiency over multiple cycles. These findings highlight the potential of Zr-di-terephthalate hybrids as sustainable, high-performance adsorbents for water purification, addressing dye contamination effectively.

UiO-67 metal-organic framework loaded on hardwood biochar for sustainable management of environmental boron contaminations

Boron contamination in water poses significant potential risks to human health and the environment, necessitating the development of efficient, cost-effective, and sustainable remediation technologies. This study introduces a novel composite material combining a zirconium-based metal-organic framework (UiO-67) and a low-cost carbonaceous material (hardwood biochar, BC) with synergetic efficiency to address boron-polluted waters. The UiO-67-biochar (UBC) composite exhibits effective surface chemistry and a remarkably high specific surface area of approximately 881.9m²/g, substantially increasing from the 19.7m²/g of biochar. Our experimental results demonstrate that UBC removed up to 88.5% of boron from 20 ppm polluted water, achieving levels compliant with the WHO standards. The composite also showed excellent reusability, maintaining 95% efficiency over multiple cycles without loss of crystallinity. Life cycle assessment and cost analysis indicate that an optimal MOF to biochar ratio of approximately 60wt% minimises CO2 emissions and costs while maximising the boron removal efficiency. The UiO-67-biochar composites proposed here offers a promising scalable solution for boron contamination and potentially other environmental pollutants, combining the high functionality of UiO-67 with the practical and economic advantages of biochar.

Controlling the Mechanism of Nucleation and Growth Enables Synthesis of UiO-66 Metal-Organic Framework with Desired Macroscopic Properties.

By combining in situ X-ray diffraction, Zr K-edge X-ray absorption spectroscopy and 1H and 13C nuclear magnetic resonance (NMR) spectroscopy, we show that the properties of the final MOF are influenced by H2O and HCl via affecting the nucleation and crystal growth at the molecular level. The nucleation implies hydrolysis of monomeric zirconium chloride complexes into zirconium-oxo species, and this process is promoted by H2O and inhibited by HCl, allowing to control crystal size by adjusting H2O/Zr and HCl/Zr ratios. The rate-determining step of crystal growth is represented by the condensation of monomeric and oligomeric zirconium-oxo species into clusters, or nodes, with the structure identical to that in secondary building units (SBU) of UiO-66 framework. The rapid crystallization in the absence of HCl leads to formation of defective secondary building units with missing zirconium atoms, providing a pathway to control the number of defects in UiO-66 crystals. Remarkably, we have shown that assembling of the metal nodes and linkers into the UiO-66 structure is not the rate-limiting step, and the degree of deprotonation of the linker has no direct effect on the crystallization kinetics or crystal size of product.

Threading MOF membranes with polymer chains for superior benzene/cyclohexane separation

High performance membranes for benzene/cyclohexane separation are crucial. Metal–organic frameworks (MOFs), given by their high structural designability, are expected to provide satisfying membrane performance for this separation. In this study, polymer chains were threaded into the pores of MOF UiO-66, to reconstruct the structures of the membrane channels. The permeance of benzene and selectivity of benzene/cyclohexane were boosted simultaneously, compared with the bare UiO-66 membranes. The performance enhancement was rationalized since the solubility of benzene was improved meanwhile the diffusivity of cyclohexane dropped by virtue of the new adsorption sites of benzene and narrower membrane channels created by threading polymers. The as-synthesized polyvinyl alcohol (PVA)-threaded UiO-66 membranes exhibited a benzene permeance around 110 GPU and a benzene/cyclohexane selectivity around 30.

Trace Adsorptive Removal of PFAS from Water by Optimizing the UiO-66 MOF Interface.

The confluence of pervasiveness, bioaccumulation, and toxicity in freshwater contaminants presents an environmental threat second to none. Exemplifying this trifecta, per- and polyfluoroalkyl substances (PFAS) present an alarming hazard among the emerging contaminants. State-of-the-art PFAS adsorbents used in drinking water treatment, namely, activated carbons and ion-exchange resins, are handicapped by low adsorption capacity, competitive adsorption, and/or slow kinetics. To overcome these shortcomings, metal-organic frameworks (MOFs) with tailored pore size, surface, and pore chemistry are promising alternatives. Thanks to the compositional modularity of MOFs and polymer-MOF composites, herein we report on a series of water-stable zirconium carboxylate MOFs and their low-cost polymer-grafted composites as C8-PFAS adsorbents with benchmark kinetics and "parts per billion" removal efficiencies. Bespoke insights into the structure-function relationships of PFAS adsorbents are obtained by leveraging interfacial design principles on solid sorbents, creating a synergy between the extrinsic particle surfaces and intrinsic molecular building blocks.

Precision management of Fusarium fujikuroi in rice through seed coating with an enhanced nanopesticide using a tannic acid-ZnII formulation

Seed coating with fungicides is a common practice in controlling seed-borne diseases, but conventional methods often result in high toxicity to plants and soil. In this study, a nanoparticle formulation was successfully developed using the metal–organic framework UiO-66 as a carrier of the fungicide ipconazole (IPC), with a tannic acid (TA)-ZnII coating serving as a protective layer. The IPC@UiO-66-TA-ZnII nanoparticles provided a controlled release, triggered and regulated by environmental factors such as pH and temperature. This formulation efficiently controlled the proliferation of Fusarium fujikuroi spores, with high penetration into both rice roots and fungal mycelia. The product exhibited high antifungal activity, achieving control efficacy rates of 84.09% to 93.10%, low biotoxicity, and promoted rice growth. Compared to the IPC flowable suspension formula, IPC@UiO-66-TA-ZnII improved the physicochemical properties and enzymatic activities in soil. Importantly, it showed potential for mitigating damage to beneficial soil bacteria. This study provides a promising approach for managing plant diseases using nanoscale fungicides in seed treatment.Graphical

Positional Isomerism: A Novel Paradigm for Enhancing Iodine Adsorption in Functionalized Metal-Organic Frameworks.

Porous metal-organic frameworks (MOFs) have shown great potential as adsorbents for capturing radioiodine, a major fission product generated during the reprocessing of nuclear fuel. However, studies exploring the correlation between the structure of MOFs and iodine uptake capacity remain notably rare. In this study, we introduce a new strategy for enhancing the iodine adsorption efficiency of MOFs by strategically varying the position of functional groups on the organic linkers. Employing ligand-functionalized UiO-67 MOFs, our findings reveal that ortho-amino substitution of UiO-67-o-NH2, proximal to the node of the dicarboxylate linker, markedly accelerates adsorption kinetics of iodine vapor in comparison to meta-amino substitution of UiO-67-m-NH2, where the amino groups are oriented away from the node. In contrast, UiO-67-m-NH2 exhibits a higher adsorption capacity of 2.19 g/g, compared to 1.91 g/g for UiO-67-o-NH2, attributable to its higher porosity. Furthermore, a competitive I2/H2O vapor adsorption study demonstrated that UiO-67-o-NH2 exhibits faster adsorption kinetics and higher selectivity for iodine in the presence of water vapor compared to UiO-67-m-NH2. Additionally, the crucial influence of positional isomerism on enhancing iodine adsorption has been corroborated through Raman spectroscopy, X-ray photoelectron spectroscopy, and density functional theory calculations. These analyses reveal that the nitrogen atom positioned at the ortho site demonstrates a stronger affinity for iodine molecules compared to the nitrogen atom at the meta site, thereby improving adsorption kinetics.

A new theory, Nanoscale Confinement Polarization Pinning effect for enhancing piezoelectricity of PVDF-HFP, to fabricate piezoelectric sensor for exercise assistance

In this study, a novel theory called Nanoscale Confinement Polarization Pinning (NCPP) theory is proposed. This theory provides theoretical support for the application of heterojunctions composed of porous metal–organic frameworks (MOFs) and conductors or semiconductors in enhancing the piezoelectric effect of piezoelectric polymers. The heterojunction formed between the metal–organic framework UIO-66(Hf)–NO2 and MoS2 enables the porous MOF to firmly pin the MoS2 onto the molecular chains of PVDF-HFP. During polarization, MoS2, being highly susceptible to the electric field, drives the movement of PVDF-HFP’s molecular chains through UIO-66(Hf)–NO2, this results in the molecular chains of PVDF-HFP aligning along the electric field, leading to a more orderly arrangement of the electric domains within PVDF-HFP and enhancing the piezoelectric effect, with the d33 value increasing from 8 pC N−1 to 27 pC N−1. The size of UIO-66(Hf)–NO2 is approximately 50 nm, with a conduction band of −0.93 eV and a bandgap of 2.56 eV, while MoS2 has a size of approximately 400 nm, a conduction band of −0.62 eV, and a bandgap of 1.27 eV. When MoS2 and UIO-66(Hf)–NO2 form a heterojunction, an interfacial electric field is generated at the junction, under the influence of this electric field, the PVDF-HFP molecular chains that penetrate into UIO-66(Hf)–NO2 tend to align, increasing the crystallinity of the composite nanofibers from 29.9 % to 35.0 %. This study broadens the application of heterojunctions formed by porous metal–organic frameworks with other conductors or semiconductors to enhance piezoelectricity, providing theoretical support.

Aliphatic amine-modified recombinant endoskeleton UiO-66 efficiently enhances CO2 capture performance

Rational chemical modification engineering of metal-organic frameworks (MOFs) is an effective means to improve their CO2 capture efficiency. In this study, we prepare UiO-66 MOF impregnated with different types of aliphatic amines using solvothermal and impregnation techniques, respectively, and investigated their performances in CO2 adsorption and CO2/N2 separation using the isothermal adsorption method. Aliphatic amines successfully chemically modifies UiO-66, and their molecules effectively occupied the pores of the UiO-66 framework, which has been confirmed by material characterization, experiments, and DFT-FMO calculations. There are significant improvements in the ability to capture CO2 when aliphatic amines were added to UiO-66 compared to pure UiO-66 (1.39 mmol/g up to 2.11 mmol/g-2.53 mmol/g), attributed to the different types and numbers of amines, and there were also differences in the Zr metal clusters and BDC ligands. Meanwhile, The material has better CO2/N2 adsorption IAST selectivity(98) because its surface area is changed and N2 does not interact specifically with the adsorbent. Furthermore, the CO2 adsorption capacity remains constant across multiple adsorption cycles, highlighting the adsorbent's stability and reliability during repetitive CO2 capture. This study provides new ideas and perspectives for improving the CO2 capture efficiency of UiO-66.

Cerium-Organic Framework UiO-66(Ce) as a Support for Nanoparticulate Gold for Use in Oxidation Catalysis.

An optimised synthesis of the metal-organic framework (MOF) UiO-66(Ce) is reported using a modulator-free route, yielding ~5 g of material with high crystallinity and 22 % ligand defect. Two methods are developed for loading gold nanoparticles onto the MOF. The first uses a double-solvent method to introduce HAuCl4 onto UiO-66(Ce), followed by reduction under 5 % H2 in N2, while the second is a novel one-pot method where HAuCl4 is added to the synthesis mixture, forming Au nanoparticles within the pores of the UiO-66(Ce) during crystallisation. Analysis using powder X-ray diffraction (PXRD), nitrogen adsorption isotherms, transmission electron microscopy and small-angle X-ray scattering (SAXS) reveals that the two-step double-solvent method yields gold crystallites on the external surface of the MOF particles that are visible by PXRD. In contrast, the one-pot method forms smaller gold crystallites, with a distribution of sizes centred on ~4 nm diameter as seen by SAXS, with evidence from PXRD for the smallest particles being present within the MOF structure. The Au-loaded UiO-66(Ce) materials are evaluated for the catalytic oxidation of vanillyl alcohol to vanillin at 60 °C. Our findings indicate that incorporating Au nanoparticles via the one-pot synthesis method, enhances redox activity, achieving 43 % conversion and 90 % selectivity towards vanillin.

Ab Initio Molecular Dynamics Investigation of Water and Butanone Adsorption on UiO-66 with Defects.

Volatile organic compounds (VOCs) are harmful chemicals that are found in minute quantities in the atmosphere and are emitted from a variety of industrial and biological processes. They can be harmful to breathe or serve as biomarkers for disease detection. Therefore, capture and detection of VOCs is important. Here, we have examined if the Zr-based UiO-66 metal-organic framework (MOF) can be used to capture butanone─a well-known VOC. Toward that end, we have performed Born-Oppenheimer ab initio molecular dynamics (AIMD) at 300 and 500 K to probe the energetics and molecular interactions between butanone [CH3C(O)CH2CH3] and open-cage Zr-UiO-66. Such interactions were systematically interrogated using three MOF structures: defective MOF with a missing 1,4-benzene-dicarboxylate linker and two H2O; pristine MOF with two H2O; and pristine dry MOF. These structures were loaded with one and four molecules of butanone to examine the effect of concentration as well. One-molecule loading interacted favorably with the defective structure at 300 K, only. In comparison, interactions with four-molecule loading were energetically favorable for all conditions. Persistent hydrogen bonds between the O atom of butanone, H2O, and μ3-OH hydroxyl attachments at Zr nodes substantially contributed to the intermolecular interactions. At higher loadings, butanone also showed a pronounced tendency to diffuse into the adjoining cages of Zr-UiO-66. The effect of such movement on interaction energies was rationalized using simple statistical mechanics-based models of interacting and noninteracting gases. Broadly, we learn that the presence of prior moisture within the interstitial cages of Zr-UiO-66 significantly impacts the adsorption behavior of butanone.

Harvesting Zr-based metal-organic frameworks by continuous-flow synthesis as efficient adsorbents for eliminating nitrogen-containing compounds in liquid fuel

This work designed a continuous-flow tubular reactor for rapidly and scalably harvesting the metal-organic framework (MOF) of UiO-66(Zr)-NH2. The experimental conditions, including temperature (110–140 °C), holding time (10–30 min), and CH3COOH/H2N-BDC molar ratio (100–250), were carried out to survey their impacts on the product yield and quality. The highest yield and production rate of ∼72% and ∼1.55 g h−1 were obtained at 130 °C, 20 min, and CH3COOH/H2N-BDC ratio 200. The temperature and modulator content significantly influenced MOFs’ crystal morphology, crystallinity, and porosity. Besides, the adopted method also successfully produced UiO-66 and UiO-67 MOFs with high production rates. The adsorptive denitrogenation (ADN) performances were carried out using liquid fuel models containing quinoline (QU) and 2-methyl pyrrole (MP). In batch mode adsorption, the UiO-66-NH2-130-200 sample showed the highest adsorbing quantities of ∼199 and ∼163 mg g−1 for QU and MP, respectively. Furthermore, the prepared MOFs efficiently removed NCCs from liquid fuel under a continuous fixed-bed column process. These demonstrate that modulator-assisted continuous-flow synthesis can be a potential strategy for the scalable harvest of Zr-MOFs with good qualities and high performance in getting rid of NCCs from liquid fuel.

Evaluation and comparison of UiO66 and its functionalized variants for the removal of Cu (II) ions from wastewater

This study examined the effectiveness of polyvinyl chloride (PVC) mixed matrix membranes incorporating UiO66 and UiO66-NH2 metal-organic frameworks (MOFs) for removing varying concentrations of Cu (II) ions from wastewater. The findings indicated that adding UiO66-NH2 to the functionalized UiO (FUiO) membrane enhanced its porosity, pore size, hydrophilicity, and pure water flux. Furthermore, integrating UiO66-NH2 into the PVC matrix led to an impressive Cu (II) ion removal efficiency exceeding 99 %. The PVC-FUiO2 membrane also demonstrated about 93.5 % reusability after the first cycle. Overall, the results confirmed that the PVC-FUiO2 (Functionalized UiO66) membrane exhibited superior performance in terms of Cu (II) removal efficiency and shorter separation times across various Cu (II) concentrations compared to the unmodified membrane.

Experimental Elucidation of a Cubane Water Cluster in the Hydrophobic Cavity of UiO-66.

Nanoscale water plays a pivotal role in determining the properties and functionalities of materials, and the precise control of its quantity and atomic-scale ordered structure is a focal point in nanotechnology and chemistry. Several studies have theoretically discussed the nano-ordered ice within one- or two-dimensional space and without confinement through hydrogen bonds. In particular, the water cluster has been predicted to play a significant role in biomolecules or functional nanomaterials; however, there has been little experimental evidence for their presence in hydrophobic cavities. In this study, the cubane water octamer - the most stable isomer among small water clusters - was detected within the hydrophobic cavities of UiO-66 metal-organic frameworks, revealing the presence of the smallest ice in their hydrophobic cavity, in the absence of hydrogen bonding. This observation contrasts earlier examples of water clusters confined within nanocavities through hydrogen bonds and provides experimental evidence for water-cluster capturing within hydrophobic cavities. Consequently, our renewed understanding of hydrophilicity and hydrophobicity warrants a design re-evaluation of materials for chemical applications, including fuel cells, water harvesting, catalysts, and batteries.

Slippery Liquid-Infused Porous Surfaces Containing UiO-66 Incorporated with 8-Hydroxyquinoline for Excellent Corrosion Protection of AZ31 Mg Alloys.

The conventional slippery liquid-infused porous surfaces (SLIPSs) provide relatively limited corrosion protection and self-healing performance for AZ31 Mg alloys. To this end, 8-hydroxyquinoline (8-HQ) was incorporated into a zirconium-based metal-organic framework UiO-66 through coordination (8-HQ@UiO-66), which was then dispersed into silicone oil to fabricate nanoparticle-enhanced-SLIPSs (8-HQ@UiO-66-SLIPSs). Especially, the influences of 8-HQ@UiO-66 concentration on the surface morphology, surface hydrophobicity, and corrosion resistance were studied. It was found that the surface hydrophobicity first increased and then decreased with increasing concentration, showing the highest water contact angle of 121.2° at a concentration of 1 mg mL-1 (8-HQ@UiO-66-SLIPS-1). This was attributed to the development of well-constructed hierarchical micro/nanostructures. Moreover, it also exhibited the best anticorrosion property, with the lowest corrosion current density of 1.24 × 10-10 A cm-2 and the highest impedance modulus of 9.88 × 108 Ω cm2 at 0.01 Hz, primarily associated with the synergistic interaction of 8-HQ and UiO-66. Further, the self-healing performance was evaluated using the scanning vibration electrode technique (SVET), verifying the superior self-healing performance of 8-HQ@UiO-66-SLIPS-1. Hence, the nanoparticle-enhanced-SLIPSs exhibit considerable potential in the corrosion protection of Mg alloys, thereby accelerating their extensive applications in industry.

CH4 Carbonylation to Acetic Acid Using H2O as an Oxidant on a Rh-Functionalized UiO-67 Combined with Oriented External Electric Fields: Selectivity and Mechanistic Insights from DFT Calculations.

Acetic acid (CH3COOH), as an industrially important petrochemical product, is predominantly produced via multistep energy-intensive processes. The development of a rhodium single-site heterogeneous catalyst has received considerable attention due to its potential to transform CH4 into CH3COOH in a single step. Herein, the reaction mechanism for the generation of CH3COOH from CH4, CO, and H2O catalyzed by Rh-functionalized metal-organic framework (MOF) UiO-67 and the selectivity of products CH3COOH, formic acid (HCOOH), methanol (CH3OH), and acetaldehyde (CH3CHO) under the oriented external electric fields (OEEFs) were systematically explored by density functional theory (DFT) calculations. The results reveal that the insertion of CO into Rh-CH3 is the rate-determining step with a free energy barrier of 21.0 kcal/mol in CH4 carbonylation to CH3COOH. Upon applying an OEEF of Fx = +0.0050 au along the C-C bond, the rate-determining step shifts toward H2O decomposition with the barrier of 19.6 kcal/mol, significantly improving the selectivity for CH3COOH production, compared to the major competitive HCOOH route. The Brønsted-Evans-Polanyi (BEP) relationships between key transition states, field strength, and NPA charge transfer were established. This study may guide the rational design of atomically dispersed MOF catalysts for the selective coconversion of CH4 and CO to CH3COOH using H2O as the oxidant under the OEEF.

Enhancing oxidative desulfurization catalytic performance of metal–organic frameworks UiO-66 (Zr) by post-synthetic with the creation of active sites

It is being explored to utilize two types of Zr-based metal–organic frameworks, bimetallic V/Zr-UiO-66 and functionalized UiO-66 by Vanadium (Zr-UiO-66-V), as heterogeneous catalysts in oxidative desulfurization processes. The bimetallic MOFs’ inorganic nodes contain two distinct ions; compared to their monometallic counterparts, these MOFs have a synergistic impact and improved characteristics. Innovative bimetallic MOFs provide additional options for further customizing the attributes of MOFs, which have drawn significant interest for various applications. On the other hand, the functionalization of MOFs further enhances the MOFs’ catalytic activity where V ions replace H+ in the –OH group in the zirconium-based node. Compared to UiO-66 (Zr), these techniques may significantly improve the efficacy of oxidative desulfurization. For the synthesized V/Zr-UiO-66 and Zr-UiO-66-V, having essential properties such as surface area (1287, 1392 m2/gr), pore volume (0.89, 0.93 cm3/gr), removal of DBT in model oil could reach > 91.4 % and > 97.7 % within 2.5 h at 343 K, respectively, which is 1.41 and 1.5 times as much as for parent UiO-66 (Zr). Furthermore, the heterogeneous catalyst displayed excellent thermal and chemical stability, and the DBT conversion efficiency remained > 78.9 % after six recycling cycles. Performance improvement is primarily attributable to the incorporation of active V sites.

UiO-67 MOF-Encapsulated NHC-Based Single-Site Copper Catalyst and Its Application in Regioselective Borylation of Terminal Alkynes.

N-Heterocyclic carbenes (NHCs) act as versatile ligand backbones due to their strong σ-donation and π-acceptance properties. However, the encapsulation of NHC-coinage metal complexes in a metal-organic framework (MOF) to utilize them in organic catalysis is rare. In this work, an NHC-coordinated CuBr (NHC = Bn2Im; 1,3-dibenzyl-imidazol-2-ylidene) complex was encapsulated in UiO-67 MOF ((Bn2Im)2CuBr@UiO-67) and further utilized toward the regioselective protoboration of terminal alkynes. (Bn2Im)2CuBr@UiO-67 was found to show superior catalytic performance in aiding the protoboration of terminal alkynes, with a very high turnover frequency (TOF) of 14333.3 h-1, much higher than those of many other reported copper-based heterogeneous catalysts. Our catalyst also retained excellent catalytic efficiency for up to five cycles for the above-mentioned process. The newly synthesized (Bn2Im)2CuBr@UiO-67 and the recovered catalyst post-catalysis were characterized using various analytical techniques, including powder X-ray diffraction (PXRD), IR spectroscopy, field-emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), and X-ray photoelectron spectroscopy (XPS).

Chitosan-polyethersulfone mixed matrix composite membranes utilizing amine and non-amine hafnium-MOFs for enhanced CO2 separation

Exploring the realm of advanced membranes with customizable separation capabilities holds great promise in CO2 separation. A particularly exciting path is the utilization of mixed matrix membranes (MMMs) to surpass the performance of commonly used polymeric membranes. In recent times, there has been a surge of interest in hafnium (Hf) metal–organic frameworks (MOFs) due to their multiple potential sites for CO2 adsorption. These MOFs feature four bridging hydroxyl groups (μ3-OH) positioned at the corners of the tetrahedral cavity, electronegative linker moieties, and Bronsted acid sites arising from undercoordinated metals. In this study, we synthesized task-specific UiO-66(Hf) and UiO-66-NH2(Hf) MOFs and integrated them into a chitosan (CS) matrix to explore their effects on CO2 separation performance of MMMs. Comprehensive analyses using various analytical techniques were conducted on synthesized MOFs and MMMs. At an optimal loading of 5 wt% of UiO-66-NH2(Hf) under humid conditions, the MMMs demonstrated a remarkable 408 % increment in CO2 permeance and a 113 % improvement in CO2/N2 selectivity compared to unfilled CS membranes. Notably, the UiO-66-NH2(Hf) MOF, enriched with amino ligands, exhibited superior dispersibility and enhanced CO2 separation ability compared to the UiO-66(Hf) MOF within the CS matrix. These findings not only approach the 2008 Robeson upper bound curve but also demonstrate consistency in the CO2 separation performance for over 120 hours of exposure at elevated temperatures (85°C) and a feed pressure of 2.21 bar under humid conditions. These challenging conditions, mirroring real-world applications, highlight the stability of the synthesized MMMs as efficient gas separation technologies.

Dispersive solid phase extraction of chloramphenicol and florfenicol in honey sample performed in narrow bore tube with the aid of magnetic ionic liquids prior to HPLC-DAD analysis

The precedence of high levels of antibiotics in animal-derived foods such as honey poses a significant food safety risk. Therefore, the development of an accurate, and reliable method for determining these residues is crucial. In this study, a new extraction method was proposed for the simultaneous determination of chloramphenicol and florfenicol residues in honey samples prior to high performance liquid chromatography analysis. The method involved using amino-functionalized UiO-66 metal–organic framework (NH2-UiO-66) as a sorbent in a narrow bore tube. To begin, the solution was placed into a narrow bore tube and the pH was adjusted to 6. Then, 100 mg of the sorbent was added to the solution. The particles were slowly passed through the solution and collected in the tube bottom. After removing the supernatant phase, 55 µL of 1-butyl-3-methylimidazolium tetrachloroferrate (III) magnetic ionic liquid was used as the elution solvent under sonication for 3 min. The optimized method exhibited low limits of detection (0.19 and 0.44 ng g−1) and quantification (0.63 and 1.4 ng g−1), good extraction recovery (81 and 74 %), and good linearity of the calibration curve (r2 ≥ 0.996) over the ranges of 1.2–500 and 2.4–500 ng g−1 for florfenicol and chloramphenicol, respectively. Precision was satisfactory, with relative standard deviations ≤8.1 % for both intra- and inter-day precisions. The developed method was done on ten honey samples and chloramphenicol was found in five samples.