Zirconium Metal Organic Framework Research Articles

Phase Engineering of Zirconium MOFs Enables Efficient Osmotic Energy Conversion: Structural Evolution Unveiled by Direct Imaging.

Creating structural defects in a controlled manner within metal-organic frameworks (MOFs) poses a significant challenge for synthesis, and concurrently, identifying the types and distributions of these defects is also a formidable task for characterization. In this study, we demonstrate that by employing 2-sulfonylterephthalic acid as the ligand for synthesizing Zr (or Hf)-based MOFs, a crystal phase transformation from the common fcu topology to the rare jmt topology can be easily facilitated using a straightforward mixed-solvent strategy. The jmt phase, characterized by an extensively open framework, can be considered a derivative of the fcu phase, generated through the introduction of missing-cluster defects. We have explicitly identified both MOF phases, their intermediate states, and the novel core-shell structures they form using ultralow-dose high-resolution transmission electron microscopy. In addition to facilitating phase engineering, the incorporation of sulfonic groups in MOFs imparts ionic selectivity, making them applicable for osmotic energy harvesting through mixed matrix membrane fabrication. The membrane containing the jmt-phase MOF exhibits an exceptionally high peak power density of 10.08 W m-2 under a 50-fold salinity gradient (NaCl: 0.5 M|0.01 M), which surpasses the threshold of 5 W m-2 for commercial applications and can be attributed to the combination of large pore size, extensive porosity, and abundant sulfonic groups in this novel MOF material.

A zirconium metal–organic framework functionalized with a S/N containing carboxylic acid (MOF-808(Zr)-Tz) as an efficient sorbent for the ultrafast and selective dispersive solid phase micro extraction of chromium, silver, and rhodium in water samples

Metal-organic frameworks (MOFs) are good adsorbents for targeted chemicals with their adjustable properties. Herein, we prepared a zirconium based MOF (MOF-808(Zr)) and functionalized it employing 2-mercapto-4-methyl-5-thiazolacetic acid (MOF-808(Zr)-Tz). The prepared MOFs were characterized by XRD, FTIR, SEM-EDX, TGA, N2 sorption, zeta potential measurements, and elemental analysis. The surface area of MOF-808(Zr)-Tz was 1348 m2/g. Dispersive solid-phase micro-extraction (D-SPµE) method based on MOF-808(Zr)-Tz was firstly developed and applied to the extraction of chromium, silver, and rhodium in waters. The determination of the analytes was done by FAAS. The optimal pH and eluent for analytes were 7.0 and 3 mL of 2 mol L−1 HCl, respectively. The contact times were 1 min for adsorption and 3 min for elution. The LOD and PFs of the D-SPμE for analytes were 2.3 μg L−1 and 13.3 for chromium, 2.1 μg L−1 and 13.3 for silver, and 3.1 μg L−1 and 13.3 rhodium, respectively. The D-SPμE method was verified with analyses of NW-TMDA-54.6 Lake water and SPS-WW1 Batch 114 Wastewater and with spiked dam water, river water, well water, sea water, and wastewater. The recoveries of the analytes changed from 89 to 108 %. The results indicated that the method is selective, simple, effective, and rapid for extracting chromium(III), silver(I) and rhodium(III) in waters.

Programmable Water Sorption through Linker Installation into a Zirconium Metal-Organic Framework.

Hydrolytically stable materials exhibiting a wide range of programmable water sorption behaviors are crucial for on-demand water sorption systems. While notable advancements in employing metal-organic frameworks (MOFs) as promising water adsorbents have been made, developing a robust yet easily tailorable MOF scaffold for specific operational conditions remains a challenge. To address this demand, we employed a topology-guided linker installation strategy using NU-600, which is a zirconium-based MOF (Zr-MOF) that contains three vacant crystallographically defined coordination sites. Through a judicious selection of three N-heterocyclic auxiliary linkers of specific lengths, we installed them into designated sites, giving rise to six new MOFs bearing different combinations of linkers in predetermined positions. The resulting MOFs, denoted as NU-606 to NU-611, demonstrate enhanced structural stability against capillary force-driven channel collapse during water desorption due to the increased connectivity of the Zr6 clusters in the resulting MOFs. Furthermore, incorporating these auxiliary linkers with various hydrophilic N sites enables the systematic modulation of the pore-filling pressure from about 55% relative humidity (RH) for the parent NU-600 down to below 40% RH. This topology-driven linker installation strategy offers precise control of water sorption properties for MOFs, highlighting a facile route to design MOF adsorbents for use in water sorption applications.

Low experimental thermal conductivity of zirconium metal-organic framework UiO-66

Using laser flash analysis, the low thermal conductivity of the pressed Zirconium metal-organic framework (UiO-66) powder pellet was obtained. As a result, the density ρ, thermal diffusivity α, specific heat capacity cP, and low thermal conductivity κexp of the pressed UiO-66 powder pellet at 300 K are observed to be 1.258 g/cm3, 0.001 59 cm2/s, 0.7765 J/g K, and 0.156 W/m K, respectively. Due to the presence of the 12-coordinated nodes with six transfer pathways, the thermal transport of the UiO-66 particles is preferred through linkers to metal sites. The low thermal conductivity follows the trend of vacuum < argon (Ar) < air < helium (He) since the entrapped gas molecules provide additional heat transfer channels inside the particles and between the particles. The low thermal conductivity along with a weak temperature-dependent thermal conductivity are elucidated in terms of boundary scattering.

UiO-66/AgNPs Coating for Dental Implants in Preventing Bacterial Infections

Titanium (Ti)–based biomaterials lack inherent antimicrobial activities, and the dental plaque formed on the implant surface is one of the main risk factors for implant infections. Construction of an antibacterial surface can effectively prevent implant infections and enhance implant success. Silver nanoparticles (AgNPs) exhibit broad antibacterial activity and a low tendency to induce drug resistance, but AgNPs easily self-aggregate in the aqueous environment, which significantly impairs their antibacterial activity. In this study, UiO-66/AgNP (U/A) nanocomposite was prepared, where zirconium metal–organic frameworks (UiO-66) were employed as the confinement matrix to control the particle size and prevent aggregation of AgNPs. The bactericidal activity of U/A against methicillin-resistant Staphylococcus aureus and Escherichia coli increased nearly 75.51 and 484.50 times compared with individually synthesized Ag. The antibacterial mechanism can be attributed to the enhanced membrane rupture caused by the ultrafine AgNPs on UiO-66, leading to protein leakage and generation of intracellular reactive oxygen species. Then, U/A was loaded onto Ti substrates (Ti-U/A) by using self-assembly deposition methods to construct an antibacterial surface coating. Ti-U/A exhibited excellent antibacterial activities and desired biocompatibility both in vitro and in vivo. The U/A nanocomposite coating technique is thus expected to be used as a promising surface modification strategy for Ti-based dental implants for preventing dental implant infections.

Non-enzymatic electrochemical impedance sensor for selective detection of electro-inactive organophosphate pesticides using Zr-MOF/ZrO2/MWCNT ternary composite

The existence of multiple pesticide residues in fruits and vegetables constitutes a direct peril to living organisms. Therefore, it is crucial to develop a low-cost screening method for determining organophosphate pesticides (OPPs) in food samples. This study describes the solvothermal synthesis of a ternary composite comprising multi-walled carbon nanotubes (MWCNT), zirconium oxide, and a zirconium-metal-organic framework (Zr-MOF). The ternary composite was characterised using XRD, FESEM, FTIR, and BET. The ternary composite provides a large surface area (1158 m2/g) compared with the pristine Zr-MOF (868 m2/g). The composite-modified glassy carbon electrode was used to determine nine pesticides, including organophosphate (malathion, dimethoate, chlorpyrifos, monocrotophos, and glyphosate) and non-organophosphate (thiophanate methyl, carbendazim, atrazine, and 2,4, D). In particular, various chemical combinations of OPPs were selected, such as S–P=S, P=S, P=O, and non-OPPs such as C=S (with sulphur), and without sulphur. The sensor results show that the sensor selectivity is high for OPPs containing both phosphorus and sulphur molecules. The low detection limit of the sensor was 2.02, 2.8, 2.5, 1.11, and 2.01 nM for malathion, chlorpyrifos, dimethoate, monocrotophos, and glyphosate, respectively. The electrode exhibited significant chemical stability (93%) after 100 cycles, good repeatability, and a long shelf life. The sensor is reliable for qualitative real-time applications.

Stepwise Node-Locking of a Mesoporous Zirconium Metal–Organic Framework Toward Enhanced Cycle Stability for Water Adsorption

Stepwise Node-Locking of a Mesoporous Zirconium Metal–Organic Framework Toward Enhanced Cycle Stability for Water Adsorption

Sequential Hydrolysis of Metal Oxo Clusters Drives Polymorphism in Electrodeposited Zirconium Metal–Organic Frameworks

Sequential Hydrolysis of Metal Oxo Clusters Drives Polymorphism in Electrodeposited Zirconium Metal–Organic Frameworks

High Capacity Arsenate Removal from Real Samples Using Dihydrotetrazine Decorated Zirconium-Based Metal-Organic Frameworks.

Zirconium metal-organic frameworks (Zr-MOFs) are potential candidates for decontamination of water resources from harmful pollutants due to their modulable porosity and chemical stability in aqueous solutions. Linker functionalization is an approach for tuning the host-guest chemistry of Zr-MOFs and extends their applications in environmental monitoring. In this work, the structure of UiO-66(Zr) (formulated Zr6(OH)4O4(BDC)6, BDC2- = benzene-1,4-dicarboxylate) was functionalized with dihydrotetrazine group via postsynthesis linker exchange (PSLE) method. The functionalized framework, UiO-66(Zr)-DHTZ, was applied for the removal of arsenate ions from aqueous solutions. The results show that UiO-66(Zr)-DHTZ can adsorb 583 mg g-1 of As(V) at pH = 7 after 2 h, which is significantly higher than that of the UiO-66(Zr). According to X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared (FTIR), the removal mechanism is based on possible hydrogen bindings between free -C-NH and -C═N- sites of dihydrotetrazine function with -O- and -OH sites of As(V) species. Removal tests in real samples show that UiO-66(Zr)-DHTZ still has a high capacity (220 mg g-1) to As(V) ions in complex matrixes and also can decrease the concentration of As(V) below the detection limit (0.05 ppm) of the inductively coupled plasma optical emission spectroscopy (ICP-OES) method. Since the dihydrotetrazine-decorated UiO-66(Zr)-DHTZ reaches one the highest adsorption capacities to As(V) species, it can be considered a potential candidate for water treatment in real-life applications.

Toxic effects and action mechanism of metal-organic framework UiO-66-NH2 in Microcystisaeruginosa

The zirconium metal-organic framework UiO-66-NH2 has garnered considerable attention for their potentials of removing environmental contaminants from water. The production and application of UiO-66-NH2 make their releases into the aquatic environment inevitable. Nevertheless, little information is available regarding its potential risk to the environment and aquatic organisms, thus limiting the evaluation of its safe and sustainable use. In this study, the ecotoxicity of UiO-66-NH2 was evaluated, specifically its impacts on growth, extracellular organic matter release, and metabolomic changes of the model phytoplankton Microcystis aeruginosa (M. aeruginosa). UiO-66-NH2 exhibited moderate effects on algal physiology including growth, viability, and photosynthetic system. At concentrations below 20 mg/L, UiO-66-NH2 induced negligible inhibition of algal growth, algal viability, and photosynthesis. In contrast, UiO-66-NH2 boosted the release of extracellular organic matter even at concentration as low as 0.02 mg/L. These findings indicated that, while no evident damage to algal cells was observed, UiO-66-NH2 was hazardous to the aquatic environment as it stimulated the release of algal toxins. Moreover, UiO-66-NH2 entered algal cells rather than adhering to the surface of M. aeruginosa as observed by the fluorescence imaging. Based on metabolic analysis, UiO-66-NH2 influenced the cyanobacteria mainly through interference with purine metabolism and ABC transporter. This study sheds light on the potential threat UiO-66-NH2 posing to microalgae, and has potential implications for its safe utilization in the environmental field.

Symmetry-Breaking Charge Transfer in Metal-Organic Frameworks.

High quantum-yield charge carrier generation from the initially prepared excitons defines a key step in the light-harvesting and conversion scheme. Photoinduced charge transfer in molecular electron donor-acceptor assemblies is driven by a sizable ΔG0, which compromises the potential of the generated carriers. Reminiscent of the special pair at the reaction center of the natural light-harvesting complex, symmetry-breaking charge transfer (SBCT) within a pair of identical struts of metal-organic framework (MOF) will facilitate the efficient generation of long-lived charge carriers with maximized potentials without incorporating any foreign redox species. We report SBCT in pyrene-based zirconium metal-organic framework (MOF) NU-1000 that leads to efficient generation of radical ions in a polar solvent and bound CT states in a low-polar solvent. The probe unveils the role of the low-lying non-Franck-Condon excitonic states as intermediates in the formation of the SBCT state from the initially prepared Franck-Condon S1 states. Ultrafast and transient spectroscopy─probed over 200 fs-30 μs time scale─evinces a kSBCT = (110 ps)-1 in polar media (εs = 37.5) forming solvated radical ions with recombination rate kCR = (∼45 ns)-1. A slower rate with kSBCT = (203 ps)-1 was recorded in low-polar (εs = 7.0) solvent manifesting a bound [TBAPy•+ TBAPy•-] state with kCR ≈ (17 μs)-1. This discovery, along with other unique photophysical features relevant to light harvesting, should define a MOF-based platform for developing heterogeneous artificial photon energy conversion systems.

Adsorption of tetracycline using one-pot synthesis zirconium metal-organic framework (UiO-66) decorated hydroxyapatite

Tetracycline (TC) is considered to be one of the commonly preferred antibiotics in the pharmaceutical industry. On the other hand, in order to eliminate the increasing environmental pollution associated with TC, the researchers are studying promising methods for its removal from water. In the present investigation, a novel zirconium metal–organic framework (UiO-66) decorated hydroxyapatite (HAp) composite adsorbent was synthesized by one-pot technique for the removal of TC from water. The proposed composites were prepared by proportioning different quantities by mass (10 %, 30 % and 50 %) of UiO-66 with HAp. The samples were characterized by various analyzes such as XRD, TGA, SEM, FT-IR and BET/N2. The adsorption process was conformed to the Langmuir isotherm model, which is a monolayer model. HAp and UiO-66@HAp composites were compared on the basis of maximum TC adsorption capacity (qmax) and the best qmax was obtained as 218.68 mg g−1 for 30UiO-66@HAp composite. Adsorption kinetics was optimized with linear pseudo second order and Elovich models, additionally the equilibrium time was determined as 300 min. Maximum adsorption was reached in the range of pH 4–8 while adsorption efficiency diminished below pH 4. Thermodynamic analysis reveals that TC adsorption is a spontaneous, favourable and endothermic process. The reusability of the 30UiO-66@HAp was perfect and the removal was 82.5 % even after 7 adsorption cycles. It also performed well with TC solutions prepared in different water matrices, with a clear reduction only with increasing HA concentration. It also showed a remarkable potential in the removal of different antibiotics and organic dyes. The synthesised 30UiO-66@HAp exhibited a favorable adsorption capacity and stable operating performance. It is expected to be utilized in the future wastewater treatment processes in industrial applications.

Highly selective carbendazim fungicide sensing performance of nitrogen-doped carbon quantum dots encapsulated aminated-UiO-66 zirconium metal-organic framework electrocatalyst

A well-known benzimidazole insecticide called carbendazim (CBM) is used in agriculture to both prevent and treat fungal plant diseases. The health of people is seriously threatened by residual CBM in water regions and food. In this study, we designed and prepared nitrogen-doped-carbon quantum dots (N-CQDs) encapsulated in zirconium metal-organic framework (MOF) UiO-66-NH2 (N-CQDs@UiO-66-NH2) electrocatalyst by facile in-situ encapsulation technique. The as-prepared electrocatalyst has been used for selective electrochemical detection of carbendazim (CBM) fungicide. The N-CQDs@UiO-66-NH2 coated screen printed electrode (SPCE) revealed a highly selective CBM detection ability with detection parameters of 0.02 – 126 µM and 5.8 nM as detection range and detection limit respectively. The highly selective CBM sensor performance of the N-CQDs@UiO-66-NH2 electrocatalyst was >95 % and the real-time minimum CBM retrieval response in vegetable and environmental water samples was 96 % and 97 % respectively.

Natural gas dehydration membranes prepared by incorporating environmentally friendly metal‐organic framework MIP‐202 into polyetherimide

AbstractUsing porous materials to selectively adsorb H2O from natural gas is a promising method to dehydrate methane (CH4). The structure of a Zirconium metal‐organic framework (Zr‐MOF), namely, MIP‐202, features a high density of amino groups, which can produce strong hydrogen bonding with H2O molecules. MIP‐202 is cost‐effective, green and scalable, and it exhibits good chemical stability under various conditions. This work incorporated MIP‐202 nanoparticles into the high permeability polymer polyetherimide (PEI), and the obtained Mixed Matrix Membranes (MMMs) was used for the gas separation of H2O/CH4. It is found that MMMs loaded with 20 wt% of MIP‐202 demonstrated a high H2O/CH4 selectivity of 832.2, which was about 760 times of that of the pure PEI. This approach offers a new route to fabricate functional membranes for energy‐efficient gas separations.

Glyme-functionalized ligand based MOF: A comprehensive study on copper and zirconium frameworks

In this study, the synthesis of a series of novel glyme-modified ligands and their corresponding copper and zirconium metal-organic frameworks (MOF) has been successfully realized. In addition, while using copper salts, it was possible to yield a water-stable MOF. Besides, the utilization of zirconium salts resulted in the formation of MOF exhibiting a UiO-68 type structure. The thorough characterization of these MOF was performed using Single Crystal X-ray Diffraction (SCXRD), Powder X-ray Diffraction (PXRD), Fourier Transform Infrared Spectroscopy (FT-IR), Scanning Electron Microscopy (SEM), Thermogravimetric Analysis (TGA) and nitrogen adsorption-desorption isotherms.Furthermore, the CO2 adsorption capacity of these MOF was also evaluated. Despite the significant differences in their crystalline networks, all MOF exhibited appreciable CO2 adsorption capacities, ranging from 0.6 to 1.3 mmol g−1 at ambient pressure and 0 °C.

Starfruit‐Shaped Zirconium Metal–Organic Frameworks: From 3D Intermediates to 2D Nanosheet Petals with Enhanced Catalytic Activity

Starfruit‐Shaped Zirconium Metal–Organic Frameworks: From 3D Intermediates to 2D Nanosheet Petals with Enhanced Catalytic Activity

Starfruit-Shaped Zirconium Metal-Organic Frameworks: From 3D Intermediates to 2D Nanosheet Petals with Enhanced Catalytic Activity.

Invited for the cover of this issue is the group of Cheng-an Tao, Jianfang Wang and co-workers at the University of Defense Technology. The image depicts a novel starfruit-shaped metal-organic framework composed of zirconium and tetra(4-carboxyphenyl)porphine linkers and characterized by 2D nanosheet petals grown through edge-sharing that showcases superior catalytic activity. Read the full text of the article at 10.1002/chem.202302835.

A Green Environmental Protection Photocatalytic Molecular Reactor for Aerobic Oxidation of Sulfide to Sulfoxide.

The design and synthesis of metal-organic frameworks (MOFs) as photocatalytic molecular reactors for varied reactions have drawn great attention. In this work, we designed a novel photoactive perylenediimides-based (PDI) carboxylate ligand N,N'-di(3',3",5',5"-tetrakis(4-carboxyphenyl))-1,2,6,7-tetrachloroperylene-3,4,9,10-tetracarboxylic acid diimide (Cl-PDI-TA) and use it to successfully synthesize a novel Zr(IV)-based MOF 1 constructed from [Zr6 O8 (H2 O)8 ]8+ clusters bridged by Cl-PDI-TA ligands. Structural analysis revealed that Zr-MOF 1 manifests a 3D framework with (4,8)-connected csq topology and possesses triangular channels of ~17 Å and mesoporous hexagonal channels of ~26 Å along c-axis. Moreover, the synthesized Zr-MOF 1 exhibits visible-light absorption and efficient photoinduced free radical generation property, making it a promising photocatalytic molecular reactor. When Zr-MOF 1 was used as a photocatalyst for the aerobic oxidation of sulfides under irradiation of visible light, it could afford the corresponding sulfoxides with high yield and selectivity. Experimental results demonstrated that the substrate sulfides could be fixed in the pores of 1 and directly transformed to the products sulfoxides in the solid state. Furthermore, the mechanism for the photocatalytic transformation was also investigated and the results revealed that the singlet oxygen (1 O2 ) and superoxide radical (O2 ⋅- ) generated by the energy transfer and electron transfer from the photoexcited Zr-MOF to oxidants were the main active species for the catalytic reactions. This work offers a perceptive comprehension of the mechanism in PDI-based MOFs for further study on photocatalytic reactions.

Starfruit-Shaped Zirconium Metal-Organic Frameworks: From 3D Intermediates to 2D Nanosheet Petals with Enhanced Catalytic Activity.

We present the fabrication of a novel Starfruit-shaped metal-organic framework (SMOF) composed of zirconium and Tetra(4-carboxyphenyl)porphine linkers. The SMOF exhibits a unique morphology with edge-sharing two-dimensional (2D) nanosheet petals. Our investigation unravels a captivating transformation process, wherein three-dimensional (3D) shuttle-shaped MOFs form initially and subsequently evolve into 2D nanosheet-based SMOF structures. The distinct morphology of SMOF showcases superior catalytic activity in detoxifying G-type nerve agent and blister agent simulants, surpassing that of its 3D counterparts. This discovery of the 3D-to-2D transition growth pathway unlocks exciting opportunities for exploring novel strategies in advanced MOF nanostructure development, not only for catalysis but also for various other applications.

Tailoring the efficiency of porphyrin molecular frameworks for the electroactivation of molecular N2.

The combination of compositional versatility and topological diversity for the integration of electroactive species into high-porosity molecular architectures is perhaps one of the main appeals of metal-organic frameworks (MOFs) in the field of electrocatalysis. This premise has attracted much interest in recent years, and the results generated have also revealed one of the main limitations of molecular materials in this context: low stability under electrocatalytic conditions. Using zirconium MOFs as a starting point, in this work, we use this stability as a variable to discriminate between the most suitable electrocatalytic reaction and specific topologies within this family. Our results revealed that the PCN-224 family is particularly suitable for the electroreduction of molecular nitrogen for the formation of ammonia with faradaic efficiencies above 30% in the presence of Ni2+ sites, an activity that improves most of the catalysts described. We also introduce the fluorination of porphyrin at the meso position as a good alternative to improve both the activity and stability of this material under electrocatalytic conditions.