Metal Organic Framework UiO-66 Research Articles

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.

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.

Exploring performance and mechanism of modified metal-organic frameworks in calcium alginate/polyvinyl alcohol double-network hydrogels for effective dye wastewater treatment

To address the growing problem of dye wastewater pollution, a novel MOFs adsorbent calcium alginate/polyvinyl alcohol@UiO-66 was developed using environmentally friendly polymers, sodium alginate and polyvinyl alcohol creating gel spheres with a double-network structure through cross-linking. UiO-66 metal-organic frameworks are then grown onto the gel spheres, resulting in the final CA/PVA@UiO-66 adsorbent. This adsorbent boasts a high surface area (17.4 m2/g) and a mesoporous-nested microporous structure. It effectively removes MB from water, the actual maximum adsorption capacity was measured at 275.8 mg/g, which surpasses most existing adsorbents. Remarkably, the adsorbent retains 93.9 % of its initial capacity even after 10 reuse cycles. The adsorption process adhered to the Redlich-Peterson model and the PFO model. The N2-Sorption isotherm, actual Methylene blue (MB) adsorption experiments, and model analysis further suggest that the adsorption process is a complex heterogeneous diffusion process involving simultaneous chemical and physical adsorption. Additionally, the adsorption process is endothermic, indicating that it can occur spontaneously at 298 K. Increasing the temperature promotes the forward progress of the adsorption reaction, thereby enhancing the adsorption capacity. The gel adsorbent exhibited excellent dye wastewater purification capabilities, coupled with commendable reusability.

Engineering the defects of UiO-66 MOF for an improved catalytic detoxification of CWA simulant: methyl paraoxon.

Exigency in search of an ideal candidate for an effective detoxification of chemical warfare agents is still continuing. Zirconium-based Metal-organic Framework (MOF) UiO-66 has shown a significant detoxification of such toxic chemicals owing to its tunable physio-chemical properties and profuse catalytic sites. In this context, a series of UiO-66 MOFs synthesized by tuning the acidity constant (pK a) and concentration of the modulator, synthesis temperature and water molecules was tested for their detoxification efficiency against the simulant 'methyl-paraoxon' at room temperature. Amongst, HCl modulated UiO-66 across the considered synthesis temperature have shown competent catalytic performance in virtue of defects generation within its structure. In addition, the role of catalytic features of UiO-66 obtained by tailoring its defects in enhancing the degradation efficiency has been systematically investigated. The detoxification efficiency of 98.5% with a half-life time of 0.23 min has confirmed the effectiveness of engineered defects in enhancing the catalytic activity of UiO-66 in detoxifying the identified simulant.

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.

Harnessing nanotechnology for breast cancer management: UiO-66 (NH2) metal-organic frameworks functionalized with chitosan and folic acid for the efficient delivery of doxorubicin

Cancer is a leading cause of morbidity globally, which could be due to a lack of effective treatments. The inherent inadequacies of traditional medicines in terms of tumour selectivity and undesired toxicity urge us to seek alternative therapies to address these drawbacks. Metalorganic frameworks (MOFs) have been synthesized for use in drug delivery systems (DDS) because of their improved porosity and larger specific surface area. In this research, UiO-66-NH2 MOFs were synthesized via a solvothermal technique and functionalized with chitosan-folic acid (CS-FA) as a DDS for targeted doxorubicin (DOX) delivery. The MOF nanoplatforms were characterized via different techniques, including FTIR, PXRD, BET, TEM, DLS, TGA, SEM, and TGA. Remarkably, compared with the unmodified MOF, UiO-DOX@CS-FA delayed DOX release due to a gated effect induced by the CS-FA surface coating. pH-sensitive DOX release was observed, where 39.76 % of the drug was released in the tumour-mimicking pH of 5.2, whereas 5.84 % of the drug was released at physiological pH (7.4). In vitro cellular toxicity and uptake investigations demonstrated that UiO-DOX@CS-FA is a highly effective targeted DDS against MCF-7 breast cancer cells. Furthermore, in vivo toxicity studies in Wistar rats revealed no evidence of serious adverse effects. The variety of pharmacokinetic characteristics tested indicated that the bioavailability and release kinetics of DOX improved. Our findings lay the groundwork for the development and production of novel polymer conjugate-based nanoparticles with increased tumour-targeting efficacy.

Enhancing the electrochemical properties of polyethylene oxide solid-state electrolytes based on a small nano-sized UiO-66 metal-organic framework

Metal-organic frameworks (MOFs) have garnered significant attention in the field of Lithium-ion batteries due to their porous periodic network properties. However, this is a challenge to design high-performance solid-state electrolytes reasonably. Herein, a small nano-sized MOF Small-UiO-66 is reported, which has high surface area and mesoporous properties that can effectively inhibit PEO matrix crystallization. The presence of Small-UiO-66 accelerates the dissociation of lithium salts, which disrupts the ordered arrangement of the PEO chain segments. The abundant Lewis acidic sites on the surface of Small-UiO-66 facilitate the construction of abundant Li+ transport channels and promote Li+ conduction. Furthermore, the smaller nano-sized increase the interfacial wettability with lithium metal, which promotes the uniform diffusion of Li+ and inhibits the growth of lithium dendrites. The results indicate that 0.1 Zr-CSE exhibits high ionic conductivities of 6.94 × 10−4 S/cm at 60 °C. Based on 0.1 Zr-CSE, the Li||Li symmetric cell can operate stably for 1200 h at a current density of 0.1 mA/cm2, and the LFP||Li cell also achieves a high initial capacity of 147.65 mAh·g−1 at current densities of 0.5C. This work presents a novel approach for preparing high-performance solid-state Lithium-ion batteries using MOFs as fillers for polymer solid-state electrolytes.

UiO-66 Inspired Superhydrophobic Coatings Fabricated from Discarded Polyester/Spandex Textiles.

We report on a method for synthesizing superhydrophobic coatings using a UiO-66 metal-organic framework (MOF) with discarded polyester/Spandex fabrics as raw materials. Unlike traditional recycling techniques that involve separating non-poly(ethylene terephthalate) (PET) components, our approach directly uses blended polyester/Spandex fibers. Discarded polyester/Spandex fabrics were exposed to an alkaline depolymerization process to produce disodium terephthalate (Na2BDC), which is a known linker for UiO-66 synthesis. We conducted experiments under two different conditions involving different amounts of ethanol. We found that with a small amount of ethanol, the resulting UiO-66 structure, when assembled on top of a polyester/Spandex substrate, exhibited a water contact angle of ≥150°─a superhydrophobic behavior. When using larger amounts of ethanol, we noted a hydrophobic behavior with a water contact angle of ∼139°. As a control, we performed the same experiments but using discarded 100% polyester fabrics as raw materials, which resulted in a superhydrophilic behavior. We attribute the superhydrophobic behavior of the UiO-66 coatings, produced from the polyester/Spandex fabrics, to the presence of hydrophobic compounds generated by the chemical degradation of Spandex. Our approach introduces a pathway for upcycling discarded textiles into superhydrophobic coatings.

Pyrolytic Depolymerization of Polyolefins Catalysed by Zirconium-based UiO-66 Metal-Organic Frameworks.

Polyolefins such as polyethylenes and polypropylenes are the most-produced plastic waste globally, yet are difficult to convert into useful products due to their unreactivity. Pyrolysis is a practical method for large-scale treatment of mixed, contaminated plastic, allowing for their conversion into industrially-relevant petrochemicals. Metal-organic frameworks (MOFs), despite their tremendous utility in heterogeneous catalysis, have been overlooked for polyolefin depolymerization due to their perceived thermal instabilities and inability of polyethylenes and polypropylenes to penetrate their pores. Herein, we demonstrate the viability of UiO-66 MOFs containing coordinatively-unsaturated zirconium nodes, as effective catalysts for pyrolysis that significantly enhances the yields of valuable liquid and gas hydrocarbons, whilst halving the amounts of residual solids produced. Reactions occur on the Lewis-acidic UiO-66 nodes, without the need for noble metals, and yield aliphatic product distributions distinctly different from the aromatic-rich hydrocarbons that can be obtained from zeolite catalysis. We also demonstrate the first unambiguous characterization of polyolefin penetration into UiO-66 pores at pyrolytic temperatures, allowing access to the abundant Zr-oxo nodes within the MOF interior for efficient C-C cleavage. Our work highlights the potential of MOFs as highly-designable heterogeneous catalysts for depolymerisation of plastics, which can complement conventional catalysts in reactivity.

Construction of nitrogen-rich groups @ zirconium-based metal-organic frameworks for efficient iodine capture

Efficient capture of radioactive iodine serves as an inevitable demand for secure utilization of nuclear energy, environmental conservation, and human health. In this contribution, a series of iodine adsorbent materials Im@UiO-66 were fabricated by encapsulating imidazole (Im) molecules into the pore of a classical zirconium-based metal–organic frameworks UiO-66, employing a simple and feasible vapor-diffusion strategy. Compared with original UiO-66, the resulting composites achieved a significant enhancement in iodine capture performance. Particularly, Im@UiO-66-3 demonstrated outstanding iodine adsorption performance with capacities of 4.66 g g−1 for vapor and 915 mg g−1 for solution, which were 3.5 and 9.2 times of the original UiO-66, respectively. Moreover, the introduction of nitrogen through ligand encapsulation provided additional sites for iodine immobilization. The primary mechanism underlying this remarkable performance was identified as charge transfer between iodine and imidazole (Im) molecules. The research offers valuable insights for the design of high-efficiency iodine adsorbents.

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 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.

Transferrin-conjugated UiO-66 metal organic frameworks loaded with doxorubicin and indocyanine green: A multimodal nanoplatform for chemo-photothermal-photodynamic approach in cancer management

Stimuli-responsive nanoplatforms have been popular in controlled drug delivery research because of their ability to differentiate the tumor microenvironment from the normal tissue environment in a spatiotemporally controllable manner. The synergistic therapeutic approach of combining cancer chemotherapy with photothermal tumor ablation has improved the therapeutic efficacy of cancer therapeutics. In this study, a UiO-66 metal organic framework (MOF)-based system loaded with doxorubicin (DOX), surface decorated with the photothermal agents indocyanine green (ICG) and polydopamine (PDA), and conjugated with transferrin (TF) was successfully designed to operate as a responsive system to pH changes, featuring photothermal capabilities and target specificity for the purpose of treating breast cancer. The synthesized nanoplatform benefits from its uniform size, excellent DOX encapsulation efficiency (91.66 %), and efficient pH/NIR-mediated controlled release of the drug. In vitro photothermal studies indicate excellent photothermal stability of the formulation even after 6 on–off cycles of NIR irradiation. The in vitro cytotoxicity assessment using an NIR laser (808 nm) revealed that the DOX-loaded functionalized UiO-66 nanocarriers had outstanding inhibitory effects on 4T1 cells because of synergistic chemo-photo therapies, with no substantial toxicity by the carriers. In addition, cellular uptake evaluations revealed that UiO-DOX-ICG@PDA-TF could specifically target 4T1 cells on the basis of receptor-mediated internalization of transferrin receptors. Additionally, in vivo toxicity studies in Wistar rats indicated no signs of significant toxicity. The UiO-based nanoformulations effectively inhibited and destroyed cancer cells under 808 nm laser irradiation because of their minimal toxicity, strong biocompatibility, and outstanding synergistic chemo/photothermal/photodynamic treatment.

UiO-67 Metal–Organic Framework as Advanced Adsorbent for Antiviral Drugs from Water Environment

Metal–organic frameworks (MOFs) have attained significant usage as adsorbents for antiviral medicines in contemporary times. This study focused on synthesizing a UiO-67 metal–organic framework using the hydrothermal method. The synthesized framework was then characterized using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), thermogravimetric analyses (TGA), and zeta potential measurements. The UiO-67 was then employed for the purpose of assessing the efficiency of various adsorption factors in the removal of antiviral medicines from aqueous solutions, including drugs such as ritonavir (RTV) and lopinavir (LPV), which were extensively used for the treatment of coronavirus (COVID-19) during the pandemic. The variables examined were the quantity of adsorbent used, different pH of the solution, temperature, and contact duration. The experimental findings indicate that the highest level of RTV elimination was 91.2% and of experimental adsorption capacity (qe,exp) was 9.7 mg/g and for LPV this was 85.9%, and (qe,exp) 8.9 mg/g, using 50 mg of UiO-67 at a pH 8, temperature of 298 K, and for 120 min. The impact of contact duration and temperature on the kinetics of adsorption was examined by employing pseudo-first-order and pseudo-second-order kinetic models. The experimental results showed a good match with the pseudo-second-order kinetic model with value of R2 0.99 and the qe,calc was 9.7 RTV and 8.9 mg/g LPV, which is a good match with qe,exp. Also, based on diffusion kinetic studies, the adsorption was confirmed to be catalytic in nature on the surface of the UiO-67 MOFs. A thermodynamic analysis of adsorption was conducted, whereby calculations for the Gibbs free energy change (∆G), enthalpy change (∆H), and entropy change (∆S) were performed. The positive ∆H values confirm the endothermic nature of the adsorption of RTV and LPV by UiO-67. The ΔG values exhibited negativity across all temperatures, suggesting the spontaneous nature of the adsorption process of RTV and LPV by UiO-67 from an aqueous solution. UiO-67 was shown to be highly effective in extracting RTV and LPV from real environmental samples.

Synthesis and Characterization of Highly Fluorinated Hydrophobic Rare-Earth Metal-Organic Frameworks (MOFs).

Tuning a material's hydrophobicity is desirable in several industrial applications, such as hydrocarbon storage, separation, selective CO2 capture, oil spill cleanup, and water purification. The introduction of fluorine into rare-earth (RE) metal-organic frameworks (MOFs) can make them hydrophobic. In this work, the linker bis(trifluoromethyl)terephthalic acid (TTA) was used to make highly fluorinated MOFs. The reaction of the TTA and RE3+ (RE: Y, Gd, or Eu) ions resulted in the primitive cubic structure (pcu) exhibiting RE dimer nodes (RE-TTA-pcu). The crystal structure of the RE-TTA-pcu was obtained. The use of the 2-fluorobenzoic acid in the synthesis resulted in fluorinated hexaclusters in the face-centered cubic (fcu) framework (RE-TTA-fcu), analogous to the UiO-66 MOF. The RE-TTA-fcu has fluorine on the linker as well as in the cluster. The MOFs were characterized by powder X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetric analysis, and contact angle measurements.

Effective removal of perfluorooctanoic acid from water using PVA@UiO-66-NH2/GO composite materials via adsorption

This study introduces an innovative approach using highly efficient nanocomposite materials to effectively remove PFAS from water, demonstrating remarkable adsorption capabilities. The nanocomposite was synthesized by integrating a zirconium-based metal-organic framework (MOF) called UiO-66 with graphene oxide (GO) within a polyvinyl alcohol (PVA) matrix. The resulting PVA@UiO-66/GO material features flower-like UiO-66 MOF crystals embedded in the PVA and GO matrix. Various kinetic models were applied to determine the rate constants and adsorption capacities, with the Langmuir isotherm indicating an adsorption capacity of 9.904 mg/g. Thermodynamic analysis confirmed the process's spontaneity and exothermic nature. The UiO-66-NH2/GO/PVA composite also demonstrated high reusability, maintaining substantial PFOA removal efficiency across multiple cycles, with optimal reduction occurring at approximately pH 5. Overall, the PVA@UiO-66/GO composites offer an effective, sustainable, and environmentally friendly solution for PFAS removal in water purification.

Partial oxidation of cyclohexene over histidine-modified Cu-UiO-66 under aerobic conditions

Enzyme-inspired catalysis is an attractive approach for developing selective hydrocarbon partial oxidation processes. Here, histidine was introduced into defective UiO-66 metal–organic framework by ligand exchange, followed by Cu(II) ion insertion. Density functional theory modeling combined with X-ray Absorption spectroscopy revealed that Cu(II) has a higher affinity for open Zr-O node sites than for histidine, leading to a series of materials where Cu(II) ions are predominantly anchored to the Zr6O4(OH)4 nodes, while only minority fractions of Cu(II) are anchored to histidine. Catalytic testing for aerobic cyclohexene oxidation with tert-butyl hydroperoxide (t-BuOOH) in trifluorotoluene solution at 25 °C showed activity for cyclohexene oxidation to cyclohexenol and cyclohexenone, with high selectivity. Benchmark tests revealed that Cu and t-BuOOH are both essential for the reaction, yet t-BuOOH consumption was far inferior to product formation rates, suggesting a radical reaction pathway involving O2.