The role of reaction temperature in the structure of Zn(II)-1,4,-Benzendicarboxylic-MOFs (Zn-BDC-MOFs) and subsequently their CO2 adsorption properties were investigated. Crystal morphology and phase structure of the Zn-BDC-MOFs were characterized by SEM and PXRD. Stability and textual properties of the Zn-BDC-MOFs were analyzed by using accelerated surface area and porosimetry apparatus (ASAP) and thermogravimetric analysis (TG). Adsorption equilibrium and diffusion of CO2 on these materials were experimentally studied by the gravimetric method in the pressure range up to 1 atm at room temperature. Results showed that reaction temperature changed the coordination mode of 1,4,-Benzendicarboxylic acid ligand and caused the different structures and pore texture of Zn-BDC-MOFs. High reaction temperature was good for the generation of the three-dimensional MOFs with a higher adsorption capacity for CO2 but lower gas diffusivity. In contrast, low reaction temperature could cause the monodentate ligand in metal centers and form the low-dimensional MOFs with a lower adsorption capacity for CO2 but higher gas diffusivity. The order of CO2 adsorption uptake and diffusion time constant were given as MOF-130T > MOF-50T > MOF-100T > MOF-75T and MOF-50T > MOF-75T > MOF-100T > MOF-130T, respectively. 相似文献
ABSTRACTMetal organic frameworks (MOFs) have become material of special attention due to their high porosity and large surface area. Adsorptive removal of ciprofloxacin hydrochloride using MOFs from aqueous waste and real wastewater has been studied in this work. The MOF-5 synthesized showed higher adsorption capacity as compared to activated charcoal. The adsorption satisfies the pseudo-second-order kinetic model and adsorption isotherm is very well explained by the Freundlich and the Sips isotherm. The adsorption mechanism may be explained by the electrostatic interactions of the pharmaceutical compounds and the MOF-5 surface. Finally, it can be concluded that MOF-5 has shown a great potential for their application in wastewater treatment technology development. 相似文献
In this research, the performance of metal–organic frameworks (MOFs) of MIL-101(Fe) and MOF-808 as aspirin detoxification agents was evaluated. MIL-101(Fe) was successfully prepared for the first time using the electrochemical method for 30 min under room temperature and pressure. MIL-101(Fe) detoxification capacity was compared to that of MOF-808, which was synthesized by a common solvothermal method at 135 °C for 24 h. The obtained materials were fully confirmed by X-ray diffraction (XRD) with the appearance of MIL-101(Fe) characteristic peaks (at 2θ 8.5°; 9°;16.7°) and MOF-808 (at 2θ 8.3°; 8.7°; 10°; 10.9°), and also confirmed by Fourier transform infrared (FTIR) spectroscopy that shows the coordination between metal and ligand. Based on scanning electron and transmission electron microscopy (SEM and TEM), MIL-101(Fe) has a micro-spindle shape with average particles size of 649.12?±?73.32 nm, while MOF-808 showed irregular shape with average particle sizes of 169.73?±?31.87 nm. Nitrogen sorption isotherm confirmed that both materials could be classified as micro to-meso porous materials by the pore radius of 1.89 nm for each materials with BET surface areas of 131 for MIL-101(Fe), and 847 m2/g for MOF-808, respectively. Based on an in vitro test, in a gastric simulation, MIL-101(Fe) decreased 11.78% of aspirin, while MOF-808 decreased 7.99%. In the intestinal simulation, MIL-101(Fe) and MOF-808 decreased aspirin by 24.06% and 26.74%, respectively. XRD analysis of the MOFs after the detoxification test showed that MIL-101(Fe) has lower stability than MOF-808. FTIR spectra confirmed that aspirin was successfully adsorbed into the MOFs. Transmission electron microscopy showed that aspirin interacted with MIL-101(Fe) on the outer surface and with MOF-808 on the inside of the pores.
A series of pyrazine-interior-embodied metal–organic framework-74 composites (py-MOF-74) were successfully synthesized by a post-synthetic vapor modification method. Here, pyrazine molecules occupy the cavity to block the wide pores of MOF-74, which accentuates the difference in adsorption of a pair of gases on MOFs and consequently reinforces the adsorption selectivity. Different from the “physical confinement” of occupants, the pyrazine molecule with dual “para-nitrogen” atoms donates one N atom to bond with the open metal ion of MOF-74 for stability and the other N atom for potential CO2 trapping. Typically, py-MOF-74c with the highest pyrazine insertion ratio displays selectivity greatly superior to that of MOF-74 in equimolar CO2/CH4 (598 vs. 35) and in simulated CO2/N2 flue gas (471 vs. 49). Py-MOF-74 entities are long-lived adsorbents, and their CO2 capacity can be maintained even after storage for 1 year in air. Py-MOF-74 also showed a sharp molecular sieve property in fixed-bed cycle adsorption tests, which implies its great potential in real applications. 相似文献
Metal-organic frameworks (MOFs), especially MOF-5, are believed to be promising new porous materials for hydrogen adsorption.
A comparative study of material synthesis, characterization and hydrogen adsorption was performed to examine the effects of
different synthesis conditions on crystal structure, pore textural property and hydrogen adsorption performance of MOF-5 materials.
Three MOF-5 samples synthesized with dimethyl formamide (DFM) as solvent and slightly different procedures have shown similar
phase structure and chemical composition, diverse crystal structures, varying pore textural properties and different hydrogen
adsorption performance. It was established from the experimental results that higher order of crystallinity in the MOF-5 materials
generates better adsorbents with larger crystal size, higher specific surface area, uniform pore size distribution (PSD),
larger hydrogen adsorption capacity and faster hydrogen diffusion rate in MOF-5 adsorbents. The best MOF-5 sample synthesized
in this work (MOF-5(γ)) has a Langmuir specific surface area of 1157 m2/g; it can adsorb 0.5 wt.% of hydrogen at 77 K and 800 mmHg; and results in hydrogen diffusivity inside MOF-5 crystal of 2.3 × 10−9 cm2/s. The density functional theory reasonably predicts the presence of mesopores and macropores in all three MOF-5 samples
synthesized in this work. 相似文献
In this study, Cu/Zn/Al2O3-AC (AC?=?activated carbon) catalyst was synthesized and evaluated for dimethoxymethane (DMM) reformation to hydrogen. The Cu/Zn/Al2O3-AC catalyst was prepared using high surface area metal organic frameworks (MOFs) consisting of Cu3(BTC)2 (MOF-199) and Zn4O(BDC)3 (MOF-5) for Cu(II) and Zn(II) sources respectively, as precursors while γ-Al2O3 was applied as support. The synthesized catalyst was investigated by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), Brunauer–Emmett–Teller analysis (BET), Temperature programmed desorption (NH3-TPD) and Energy-dispersive X-ray spectroscopy (EDX) techniques. Complete DMM conversion was observed over Cu/Zn/Al2O3-AC catalyst (Cu:Zn:Al mole ratio of 6:3:2) under atmospheric pressure, T?=?533 K, GHSV?=?20 NL h?1 gcat?1, N2/H2O/DMM?=?24/5/1 volume percent (vol%) with hydrogen productivity of 12.8 L H2 h?1 gcat?1 and 64% hydrogen concentration. Application of MOFs as precursors and modified activated carbon as an acidic component provided the catalyst with the porous structure and high specific surface area for the hydrolysis of DMM, subsequently, high selectivity and productivity of hydrogen was obtained. 相似文献
Synthesized iron-terephthalate metal–organic frameworks (MOFs), MIL-101 and MOF-235, with contrasting morphologies are examined to elucidate the role of structural arrangement in catalytic aqueous pollutant degradation. MIL-101 demonstrates a larger pseudo-first order rate constant than MOF-235 (3.5 ± 0.2 molFe−1 · s−1 vs. 0.84 ± 0.07 molFe−1 · s−1) toward oxidation of methylene blue (MB) dye with excess hydrogen peroxide at ambient temperature, likely due to intrinsic differences in ligand coordination at their metal nodes. However, despite continued activity upon reuse, both MOFs undergo structural alterations resulting in formation of leached species active for MB degradation that have been obfuscated in previous studies. Detailed stability testing and ex situ characterization of recovered catalyst, examinations that remain underreported in Fe-MOF studies for pollutant oxidation, indicate that water plays a prominent role in the breakdown of these frameworks. Collectively, this work informs the interpretation and use of common Fe-MOFs for aqueous applications, relating material changes to observed reaction phenomena. 相似文献
A new mixed-valent iron MOF, formulated as Fe3O(F4BDC)3(H2O)3·(DMF)3.5 (1), has been synthesized by using a perfluorinated linear dicarboxylate to link trigonal prismatic Fe3(μ3-O)(O2C–)6 clusters. The structure refinement based on single crystal X-ray diffraction data collected from 1 reveals the material exhibits the acs topology with large channels along the crystallographic c-axis. Due to the presence of fluorine atoms the organic link, 2,3,5,6-tetrafluorobenzene-1,4-dicarboxylate (F4BDC), has a 63° torsion angle between the carboxylate and aromatic planes, resulting in larger channels compared to those in the isoreticular material MOF-235. While few iron-based MOFs have demonstrated porosity, nitrogen and hydrogen sorption experiments carried out at 77 K proved the porosity of outgassed 1, which has a Langmuir surface are of 635 m2/g and a gravimetric capacity of 0.9 wt% of hydrogen at 1 bar. 相似文献
In modern analytical chemistry researchers pursue novel materials to meet analytical challenges such as improvements in sensitivity, selectivity, and detection limit. Metal-organic frameworks (MOFs) are an emerging class of microporous materials, and their unusual properties such as high surface area, good thermal stability, uniform structured nanoscale cavities, and the availability of in-pore functionality and outer-surface modification are attractive for diverse analytical applications. This Account summarizes our research on the analytical applications of MOFs ranging from sampling to chromatographic separation. MOFs have been either directly used or engineered to meet the demands of various analytical applications. Bulk MOFs with microsized crystals are convenient sorbents for direct application to in-field sampling and solid-phase extraction. Quartz tubes packed with MOF-5 have shown excellent stability, adsorption efficiency, and reproducibility for in-field sampling and trapping of atmospheric formaldehyde. The 2D copper(II) isonicotinate packed microcolumn has demonstrated large enhancement factors and good shape- and size-selectivity when applied to on-line solid-phase extraction of polycyclic aromatic hydrocarbons in water samples. We have explored the molecular sieving effect of MOFs for the efficient enrichment of peptides with simultaneous exclusion of proteins from biological fluids. These results show promise for the future of MOFs in peptidomics research. Moreover, nanosized MOFs and engineered thin films of MOFs are promising materials as novel coatings for solid-phase microextraction. We have developed an in situ hydrothermal growth approach to fabricate thin films of MOF-199 on etched stainless steel wire for solid-phase microextraction of volatile benzene homologues with large enhancement factors and wide linearity. Their high thermal stability and easy-to-engineer nanocrystals make MOFs attractive as new stationary phases to fabricate MOF-coated capillaries for high-resolution gas chromatography (GC). We have explored a dynamic coating approach to fabricate a MOF-coated capillary for the GC separation of important raw chemicals and persistent organic pollutants with high resolution and excellent selectivity. We have combined a MOF-coated fiber for solid-phase microextraction with a MOF-coated capillary for GC separation, which provides an effective MOF-based tandem molecular sieve platform for selective microextraction and high-resolution GC separation of target analytes in complex samples. Microsized MOFs with good solvent stability are attractive stationary phases for high-performance liquid chromatography (HPLC). These materials have shown high resolution and good selectivity and reproducibility in both the normal-phase HPLC separation of fullerenes and substituted aromatics on MIL-101 packed columns and position isomers on a MIL-53(Al) packed column and the reversed-phase HPLC separation of a wide range of analytes from nonpolar to polar and acidic to basic solutes. Despite the above achievements, further exploration of MOFs in analytical chemistry is needed. Especially, analytical application-oriented engineering of MOFs is imperative for specific applications. 相似文献
A systematic molecular simulation study was performed to investigate the effect of catenation on methane adsorption in metal-organic frameworks (MOFs). Four pairs of isoreticular MOFs (IRMOFs) with and without catenation were adopted and their capacities for methane adsorption were compared at room temperature. The pre-sent work showed that catenation could greatly enhance the storage capacity of methane in MOFs, due to the for-mation of additional small pores and adsorption sites formed by the catenation of frameworks. In addition, the simulation results obtained at 298 K and 3.5 MPa showed that catenated MOFs could easily meet the requirement for methane storage in porous materials. 相似文献
In this work grand canonical Monte Carlo simulations were performed to study gas separation in three pairs of isoreticular metal-organic frameworks (IRMOFs) with and without catenation at room temperature. Mixture composed of CO2 and H2 was selected as the model system to separate. The results show that CO2 selectivity in catenated MOFs with multi-porous frameworks is much higher than their non-catenated counterparts. The simulations also show that the electrostatic interactions are very important for the selectivity, and the contributions of different electrostatic interactions are different, depending on pore size, pressure and mixture composition. In fact, changing the electrostatic interactions can even qualitatively change the adsorption behavior. A general conclu-sion is that the electrostatic interactions between adsorbate molecules and the framework atoms play a dominant role at low pressures, and these interactions in catenated MOFs have much more pronounced effects than those in their non-catenated counterparts, while the electrostatic interactions between adsorbate molecules become evident with increasing pressure, and eventually dominant. 相似文献
Metal-organic frameworks (MOFs)-highly crystalline hybrid materials that combine metal ions with rigid organic ligands-have emerged as an important class of porous materials. The organic ligands add flexibility and diversity to the chemical structures and functions of these materials. In this Account, we summarize our laboratory's experience in tuning the topology and functionality of MOFs by ligand design. These investigations have led to new materials with interesting properties. By using a ligand that can adopt different symmetry conformations through free internal bond rotation, we have obtained two MOFs that are supramolecular stereoisomers of each other at different reaction temperatures. In another case, where the dimerized ligands function as a D(3)-Piedfort unit spacer, we achieve chiral (10,3)-a networks. In the design of MOF-based materials for hydrogen and methane storage, we focused on increasing the gas affinity of frameworks by using ligands with different geometries to control the pore size and effectively introduce unsaturated metal centers (UMCs) into the framework. Framework interpenetration in PCN-6 (PCN stands for porous coordination network) can lead to higher hydrogen uptake. Because of the proper alignment of the UMCs, PCN-12 holds the record for uptake of hydrogen at 77 K/760 Torr. In the case of methane storage, PCN-14 with anthracene-derived ligand achieves breakthrough storage capacity, at a level 28% higher than the U.S. Department of Energy target. Selective gas adsorption requires a pore size comparable to that of the target gas molecules; therefore, we use bulky ligands and network interpenetration to reduce the pore size. In addition, with the help of an amphiphilic ligand, we were able to use temperature to continuously change pore size in a 2D layer MOF. Adding charge to an organic ligand can also stabilize frameworks. By ionizing the amine group within mesoMOF-1, the resulting electronic repulsion keeps the network from collapsing, giving rise to the first case of mesoporous MOF that demonstrates the type IV isotherm. We use dendritic hexacarboxylate ligands to synthesize an isoreticular series of MOFs with (3,24)-connected network topology. The cuboctahedral cages serve as building blocks that narrow the opening of the mesocavities into microwindows and stabilize these MOFs. The resulting materials have exceptionally high surface areas and hydrogen uptake capacities. Despite the many achievements in MOF development, there is still ample opportunity for further exploration. We will be continuing our efforts and look forward to contributing to this blossoming field in the next decade. 相似文献
Hydrogen adsorption mechanism into MOF-5, a porous metal-organic framework (MOF) has been studied by density functional theory calculation. The selected functionals for the prediction of interaction energies between hydrogen and potential adsorption sites of MOF-5 were utilized after the evaluation with the various functionals for interaction energy of H2C6H6 model system. The adsorption energy of hydrogen molecule into MOF-5 was investigated with the consideration of the favorable adsorption sites and the orientations. We also calculated the second favorable adsorption sites by geometry optimization using every combination of two first adsorbed hydrogen molecules. Based on the calculation of the first and the second adsorption sites and energies, it has been suggested that the hydrogen adsorption into MOF-5 follows a cooperative mechanism in which the metal sites initiate the propagation of the hydrogen adsorption on the whole frameworks. In addition, the interaction mode between the simple benzene ring with hydrogen is significantly changed when the benzene ring has been incorporated into the framework of MOF-5. 相似文献