CN115975211B - Mesoporous zirconium-based metal organic framework with high water stability, and synthetic method and application thereof - Google Patents
Mesoporous zirconium-based metal organic framework with high water stability, and synthetic method and application thereof Download PDFInfo
- Publication number
- CN115975211B CN115975211B CN202310076055.XA CN202310076055A CN115975211B CN 115975211 B CN115975211 B CN 115975211B CN 202310076055 A CN202310076055 A CN 202310076055A CN 115975211 B CN115975211 B CN 115975211B
- Authority
- CN
- China
- Prior art keywords
- organic framework
- metal organic
- zirconium
- based metal
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a mesoporous zirconium-based metal organic framework with high water stability, and a synthesis method and application thereof, and belongs to the technical field of water adsorption metal organic framework compounds. The invention successfully synthesizes the isomer of NU-1000 containing mesopores with closed c-holes, and the novel isomer has better water stability, water vapor absorption capacity and cycle stability, so that the isomer can be applied to a heat conversion system based on the water vapor absorption principle. The high water circulation stability of the metal organic framework compound in the invention is mainly that the closed c hole of the metal organic framework compound prevents the hydrolysis of metal node coordination formate in the c hole area, thereby preventing the introduction of ligands such as water on the metal node, terminal hydroxyl and the like.
Description
Technical Field
The invention belongs to synthesis of metal organic framework materials, and particularly relates to a isomorphic metal organic framework material with one-dimensional mesoporous channels, which is constructed by tetravalent metal ion clusters and is based on 1,2,6, 7-tetra (4-carboxybenzene) pyrene as a ligand.
Background
With the development of human society and the improvement of living standard, the demand of human for energy in indoor temperature control is further increased. Currently, vapor compression systems required for indoor temperature control are severely dependent on electrical energy, contrary to the current large goal of global curtailment of fossil energy consumption. Therefore, development of energy saving technology, especially green renewable energy, is highly necessary. As an efficient and environment-friendly technology, a heat conversion system based on the principle of water adsorption is receiving a great deal of attention because it can well utilize low-grade energy or solar energy as a basic energy source.
The metal organic framework compound is used as an ordered crystalline porous material with high specific surface area and large pore volume, and the structure and the components can be accurately regulated and controlled, and has excellent application prospect in the field of heat conversion based on the water adsorption principle. At present, the design and synthesis of stable metal-organic framework materials with high water adsorption capacity are very popular research directions. Based on the theory of hardness and softness, the high-valence transition metal (such as Al 3+ , Cr 3+ , Zr 4+ , Fe 3+ , Hf 4+ Etc.) are susceptible to forming strong coordination bonds with carboxylic acid ligands, and thus show particular advantages in the construction of highly stable metal-organic frameworks. Wherein the alloy is made of tetravalent metal zirconiumAnd hafnium-built zirconium-based and hafnium-based metal organic frameworks have received great attention. Taking zirconium-based metal-organic framework materials as an example, these materials can be classified into two classes according to different water adsorption mechanisms: 1) Microporous zirconium-based metal-organic framework materials having pore sizes less than 2nm generally have reversible adsorption behavior and tend to maintain structural stability during continuous pore filling; 2) Mesoporous zirconium-based metal organic framework material with aperture larger than 2nm can be influenced by capillary force in desorption process, so that structure collapse phenomenon occurs in irreversible adsorption and desorption process. Thus, it remains a challenge for mesoporous zirconium-based and hafnium-based metal organic frameworks to enhance the resistance of the materials to capillary force failure, thereby improving the cycling stability of the materials. The NU-1000 metal organic aggregate disclosed in the prior art [ non-patent document 1 ] is a typical zirconium-based MOF, has a 1D mesoporous channel and csq topological structure, and has application prospects in applications involving guest molecule transmission, chemical separation and/or chemical catalysis; however, capillary forces drive the channel collapse during removal of water in further cycles. Later studies showed that the cyclic stability of NU-1000 can be enhanced by introducing hydrophobic carboxylate for node functionalization, but there is a significant sacrifice in porosity and water absorption capacity [ non-patent document 2 ].
Non-patent document 1: mondlock, J.E., bury, W., fairen-Jimez, D., kwon, S., deMarco, E.J., weston, M.H., sarjeant, A.A., nguyen, S.T., star, P.C., snurr, R.Q., farha, O.K., hupp, J.T., vapor-phase metalation by atomic layer deposition in a metal-organic framework J. Am. chem, soc.2013, 135 (28), 10294-7.
Non-patent document 2: deria, P., chung, Y.G., snurr, R.Q., hupp, J.T., farha, O.K., water stabilization of Zr-based metal-organic frameworks via solvent-based bond in corporation, chem. Sci.2015, 6 (9), 5172-5176.
Disclosure of Invention
A first object of the present invention is to provide a hafnium-based and zirconium-based two isomorphic forms of metal organic framework materials with high cyclic adsorption stability that can be used in a thermal conversion system based on the water adsorption principle;
the second object of the present invention is to provide a method for synthesizing the metal-organic framework material;
a third object of the present invention is to provide an application of the above-mentioned metal-organic framework in a heat conversion system based on the principle of water adsorption;
m formed by tetravalent metal ions 6 (μ 3 -O) 4 (μ 3 -OH) 4 (HCOO) 4 The metal clusters are used as nodes, 1,2,6, 7-tetra (4-carboxylbenzenepyrene) is used as an organic ligand, the solvent is N, N-dimethylformamide, and a metal organic framework material with one-dimensional mesoporous channels is synthesized by a solvothermal method.
Mesoporous zirconium/hafnium-based metal organic framework compound with general formula of C 92 H 36 O 32 M 6 M represents metal Zr or Hf, and 1,2,6, 7-tetra (4-carboxybenzene) pyrene is used as ligand, all carboxylic acid groups in the ligand participate in coordination, and M is formed by M metal ions 6 (μ 3 -O) 4 (μ 3 -OH) 4 (HCOO) 4 The metal cluster has skeleton structure of one-dimensional mesoporous pore canalcsqTopology type three-dimensional network structure.
The mesoporous zirconium/hafnium-based metal organic framework compound has the lattice characteristics of a hexagonal system, and the space group isP6/mmm。
The unit cell parameters of the mesoporous zirconium/hafnium-based metal organic framework compound are respectively as followsa=b= 45.6079 Å，c= 13.0998 Å，α=β= 90°，γ= 120°。
Edge of the framecThe axial direction comprises one-dimensional hexagonal mesoporous channels with the diameter of 3.2nm and triangular microporous channels with the diameter of 1.2 nm.
The synthesis method of the mesoporous zirconium/hafnium-based metal organic framework compound comprises the following steps:
step (1): dissolving M metal salt in an organic solvent, adding formic acid to dissolve completely and preheating;
step (2): adding ligand 1,2,6, 7-tetra (4-carboxybenzene) pyrene into an organic solvent, and dissolving after preheating;
step (3): mixing the solutions obtained in the step (1) and the step (2), adding formic acid again, then carrying out solvothermal reaction, and cooling after finishing to obtain light yellow powder crystals;
step (4): finally, washing and drying to obtain the metal organic framework.
The organic solvent is N, N-dimethylformamide.
The M metal salt is selected from one of zirconium oxychloride octahydrate or hafnium oxychloride octahydrate.
In the step (1), when the zirconium-based metal organic framework is synthesized, the dosage ratio of the zirconium oxychloride octahydrate to the organic solvent and formic acid is 25 milligrams: 1-3 milliliters: 100 to 400 microliters, preferably 25 milligrams: 1.5 ml: 280 microlitres.
In the step (1), when synthesizing the hafnium-based metal organic skeleton, the dosage ratio of the octahydrated hafnium oxychloride to the organic solvent and formic acid is 30 mg: 1-3 milliliters: 100 to 400 microliters, preferably 30 milligrams: 1.5 ml: 280 microlitres.
In the step (1), the preheating temperature is 70-90 ℃ and the preheating time is 1-2 hours.
The molar ratio of ligand 1,2,6, 7-tetrakis (4-carboxylbenzenepyrene and metal salt shown in steps (1) and (2) is 1: 3-9.
The dosage ratio of the ligand 1,2,6, 7-tetra (4-carboxylbenzenepyrene) to the organic solvent in the step (2) is 10 mg: 1-3 ml, preferably 10 mg: 1 ml.
In the step (2), the preheating temperature is 70-90 ℃ and the preheating time is 1-2 hours.
The formic acid used in the step (3) is 100 to 300. Mu.l, preferably 200. Mu.l.
In the step (3), the temperature of the solvothermal reaction is 110-130 ℃ and the reaction time is 1-2 days.
The invention further protects the application of the metal-organic framework with two isomorphic forms of hafnium base and zirconium base in a water vapor adsorption and water adsorption principle-based heat conversion system.
Advantageous effects
Chemically and hydrolytically stable MOFs show great potential in many applications related to water adsorption. However, it is rare to have a large pore MOF. By deliberate modification of the organic ligand of a typical zirconium-based MOF (NU-1000), a block was successfully synthesizedcMesoporous metal-organic framework compounds, which exhibit high water absorption capacity and high hydrolytic and mechanical cycling stability, make them very promising candidates for water vapor adsorption-based applications such as water adsorption-driven heat transfer.
The high water circulation stability can be attributed to its blockingcHoles, which prevent the position ofcThe hydrolysis of the coordination formate of the metal node in the pore region prevents the introduction of ligands such as water and terminal hydroxyl groups on the metal node. Without these ligands and their ability to hydrogen bond with water molecules located in the pore channels, the intensity of the guest (water)/host (MOF) interaction is diminished, and the absolute magnitude of capillary forces generated by the water exiting the MOF channels is therefore also diminished. This decay enables the MOF to resist pore collapse, capacity loss, and crystallinity loss during repeated evaporative removal (and reintroduction) of water from the pores.
Drawings
FIG. 1 is a schematic diagram of the synthesis and crystal structure of the ISO-NU-1000 zirconium/hafnium-based metal organic framework material and NU-1000 of the present invention.
FIG. 2 is a single crystal electron micrograph of a zirconium-based metal organic framework material.
Fig. 3 is a powder electron micrograph of a zirconium-based metal organic framework material.
FIG. 4 is a graph comparing X-ray powder diffraction patterns of zirconium/hafnium-based metal organic frameworks with crystalline simulated X-ray powder diffraction patterns.
FIG. 5 is a PXRD pattern for simulated ISO-NU-1000, experimental ISO-NU-000 and NU-1000.
FIG. 6 is ISO-NU-1000 and N of NU-1000 measured at 77K 2 Adsorption curve and pore size distribution.
FIG. 7 shows the respective water flowsAnd acetone activated ISO-NU-1000 and N of NU-1000 2 Adsorption curve.
FIG. 8 is a) water adsorption curve for the first three cycles NU-1000; b) Two-point cycling stability test for NU-1000, P/p0=0.2 and 0.8; c) An ISO-NU-1000 initial three cycle water adsorption curve; d) Two-point cycling stability test for ISO-NU-1000, P/p0=0.2 and 0.8.
FIG. 9 is a DRIFTS spectrum of NU-1000 and ISO-NU-1000 before and after 22 cycles of water adsorption and desorption.
FIG. 10 is ISO-NU-1000 after the cycling stability test 1 H NMR spectra, each Zr 6 The node contains 2.64 formate groups (8.371 ppm).
FIG. 11 is NU-1000 after a cycling stability test 1 H NMR spectra, each Zr 6 The node contains 2.38 formate groups (8.371 ppm).
FIG. 12 is a graph of NU-1000 after a cyclic stability test and 5h immersion in water 1 H NMR spectra, each Zr 6 The node contains 0.88 formate (8.371 ppm).
FIG. 13 is a graph of ISO-NU-1000 after a cyclic stability test and 5h of immersion in water 1 H NMR spectra, each Zr 6 The node contains 2.26 formate groups (8.372 ppm).
FIG. 14 is an SEM image of NU-1000 after a cyclic stability test.
FIG. 15 is a nitrogen adsorption line for NU-1000 before and after the cycling stability test.
FIG. 16 is a PXRD pattern for NU-1000 before and after the cycling stability test.
Description of the embodiments
Examples
The synthesis step of the zirconium-based metal organic framework comprises the following steps:
(1) Zirconium oxychloride octahydrate (25 mg) was dissolved in N, N-dimethylformamide (1.5 ml), formic acid (280 μl) was added, and the dissolution was completed by ultrasonic vibration, and heated at 80 ℃ for one hour;
(2) Ligand 1,2,6, 7-tetra (4-carboxybenzene) pyrene (10 mg) was added to N, N-dimethylformamide (1 ml), and ultrasonic vibration was performed to obtain a suspension, and the suspension was heated at 80℃for one hour simultaneously with the metal salt solution in 1), at which time the ligand was completely dissolved;
(3) Mixing the solutions obtained in (1) and (2) into a polytetrafluoroethylene-lined reaction kettle, adding formic acid (200 microliters) again, then carrying out constant-temperature solvothermal reaction at 120 ℃ for 12 hours, and cooling to room temperature after finishing to obtain pale yellow powder crystals;
(4) Centrifuging to collect the pale yellow powder crystal, washing for many times by using N, N-dimethylformamide and acetone, and drying at 65 ℃ for one hour to obtain a final metal organic framework material;
the chemical general formula of the zirconium-based metal organic framework material can be written as C 92 H 36 O 32 Zr 6 1,2,6, 7-tetra (4-carboxybenzene) pyrene is used as ligand to construct and is crystallized in a hexagonal system,P6/mmmspace group, unit cell parameters are respectivelya=b= 45.6079 Å，c= 13.0998 Å，α=β= 90°，γ=120°. The carboxylic acid groups in the ligand are all involved in coordination, zr formed with tetravalent metal ions 6 (μ 3 -O) 4 (μ 3 -OH) 4 (HCOO) 4 The metal clusters together construct a three-dimensional space structure with a hexagonal topology type penetrating through the mesopores. The through regular hexagonal channel is positionedcIn the axial direction, the size is 3.2nm of diameter, six small triangular through passages are arranged around the axial direction, and the size is 1.2 nm of diameter.
Comparative example 1:
preparation of NU-1000 materials for comparison (Mondloch, J.E.; bury, W.; faire-Jimez, D.; kwon, S.; deMarco, E.J.; weston, M.H.; sarjeant, A.A.; nguyen, S.T.; star, P.C.; snurr, R.Q.; farha, O.K.; hupp, J.T.; vapor-phase metalation by atomic layer deposition in a metal-organic framework, J. Am. chem. Soc.2013, 135 (28), 10294-7.).
Briefly, zrOCl of 98 mg 2 ·8H 2 The O and 2 g benzoic acid were dissolved in 8 mL DMF solution and then heated in an oven at 100 ℃ for 1 hour. After cooling to room temperature, 40 mg H was added 4 TBAPy and 40. Mu.L trifluoroacetic acid (TFA) and sonicated for 10 min, the resulting suspension was reacted in an oven at 120℃for 18 hours to give a yellow polycrystalline precipitate. The precipitate was washed thoroughly three times with DMF and then dispersed in 15mL of DMF and 0.6mL of 8M aqueous HCl. The mixture was heated in an oven at 100 ℃ for 18 hours. After cooling to room temperature, the solid was separated by centrifugation and washed with DMF for 8 hours. To characterize the porosity, the powder samples were exchanged three times with acetone solvent and soaked in acetone for an additional 16 hours. NU-1000 samples were collected by centrifugation and dried in vacuo. Dynamic vacuum activation was then carried out at 120℃for 18 hours to give a yellow powder.
Characterization of the metal organic framework structure:
by using Zr 6 (μ 3 -O) 4 (μ 3 -OH) 4 (HCOO) 4 Nodes and tetracarboxylic acid linkages to mimic zirconium MOF structures. The structure was determined by calculation from the PXRD pattern of ISO-NU-1000 prepared in example 1 (FIG. 5). Because of the similarity of crystal shape and building blocks, ISO-NU-1000 can be considered to have a structure similar to NU-1000, and thus, a structural model of ISO-NU-1000 is constructed based on building blocks of NU-1000: 1) Use of a Metal node Zr with eight-connectivity and four formate ligands similar to NU-1000 6 (μ 3 -O) 4 (μ 3 -OH) 4 (HCOO) 4 The method comprises the steps of carrying out a first treatment on the surface of the 2) The terminal benzoic acid was transferred from carbon atoms No. 1, 3, 6 and 8 to carbon atoms No. 4, 5, 9 and 10 of the pyrene ring without changing the dihedral angle between the terminal benzene ring and the central pyrene ring. Corresponding MOF molecular building blocks were created using the Crystal building block using Materials Studio software and placed in the appropriate placecsqAnd a lattice template. The building block again corresponds to a metal node into which these eight carboxylic acid groups have been incorporated for ease of calculation. The analog structure consists of 8-linked Zr 6 Node and 4-connected H 4 TBAPy-2 linker composition havingcsqNetwork topology. ISO-NU-1000 is an isomer of NU-1000 because they not only have the same topology but also use the same Zr 6 Node and same-differentAn organic linker is constructed (FIG. 1). Notably, the diameter of the hexagonal pores (3.2 nm) in ISO-NU-1000 is larger than that of the hexagonal pores (2.9 nm) in NU-1000 due to the shift of the position of the terminal benzoic acid ring on the pyrene nucleus. Most importantly, for two types of windows between ISO-NU-1000 hexagonal and triangular holescThe pores were 0.64X 0.08nm,c' pores, 0.90×0.24nm; FIG. 1) are all much smaller than the window of NU-1000cPores 0.90×0.44nm;c' pores 0.66×0.54 nm). These narrow windows are smaller than the kinetic diameter of water molecules, impeding the diffusion of water molecules between mesopores and micropores.
As shown in fig. 6, to characterize the porosity of ISO-NU-1000, a powder sample thereof was subjected to solvent exchange with acetone and further vacuum-pulled at 120 ℃ for 16 hours to obtain an activated sample. Compared with NU-1000, ISO-NU-1000N 2 Isotherms are higherP/P 0 (-0.32) and lower saturation N 2 Absorption (800 cm) 3 g -1 ) A steep curve is shown. According to N 2 Isotherms (FIG. 6), BET surface area of ISO-NU-1000 was 1730m 2 g -1 Slightly lower than NU-1000 (2170 to cm) 3 g -1 ). According to N 2 The Pore Size Distribution (PSD) calculated by isotherm shows that mesopores (3.0-3.7 nm) and micropores (1.1-1.5 nm) exist in ISO-NU-1000 and are consistent with the crystal structure of the mesoporous (3.0-3.7 nm). Based on N 2 Isothermal calculation of the total pore volume of ISO-NU-1000 of 1.27cm 3 g -1 。
Stability of ISO-NU-1000:
n was performed by immersing the sample in water for 24 hours and directly activating from the water 2 Adsorption test (fig. 7). The BET surface area of ISO-NU-1000 activated from water was found to be 1720m 2 g −1 This is almost the same as activation from acetone, maintaining its high porosity and surface area. As a comparison, NU-1000 activated from water in comparative example 1 showed partial degradation of the structure. This result shows that ISO-NU-1000 is a highly porous material with ultra high mechanical and chemical hydrolytic stability.
Water vapor adsorption performance:
advancing oneThe water adsorption performance at 298K was tested. As shown in FIG. 8 a, NU-1000 is betweenP/P 0 Shows steep absorption at=0.6, showing pore filling or water coagulation into the pores. Although the initial saturated water absorption is 1490 and 1490 cm 3 g -1 However, in further cycles, the water uptake drops sharply, reaching only about 705 cm near saturation 3 g -1 . In contrast, ISO-NU-1000 is characterized in that it has relatively large mesoporesP/P 0 At a higher partial pressure of =0.65, steep absorption was exhibited. Its initial saturated uptake was 1370 cm 3 g -1 （1.1g g -1 C) of fig. 8, the further cycle showed no significant decrease, and the approximate value of near saturation in the third cycle was 1360 cm 3 g -1 . Further examine the multi-cycle stability of ISO-NU-1000 in another 19 two-point cyclesP/P 0 =0.2 and 0.8). After a total of 22 cycles of the process,P/P 0 the water vapor adsorption capacity at=0.8 is almost the same as that of the first cycle (d of fig. 8). In contrast, NU-1000 exhibits very low water absorption after three complete cycles (atP/P 0 Less than 300 cm when=0.8 3 g -1 ) (b of FIG. 8). These results indicate that ISO-NU-1000 is a good candidate for steam adsorption based applications such as thermal conversion of water adsorption. Meanwhile, it is also the first zirconium-based MOF containing the largest mesopores that is capable of maintaining excellent steam stability at present. The difference in water stability between ISO-NU-1000 and NU-1000 results fromcStructural differences in the pore areas. Stenosis in ISO-NU-1000 blocked by formate groups involved in coordinationcThe pores block the passage of water molecules and thus the hydrolysis of formate.
The formate status in the sample after water adsorption was confirmed by the following method: after multiple water adsorption and desorption cycles, the presence/state of formate in NU-1000 and ISO-NU-1000 was evaluated. As shown by the Diffuse Reflection Infrared Fourier Transform (DRIFT) spectrum (FIG. 9), NU-1000 was initially 2745cm after 22 cycles of water adsorption and desorption -1 Formate C-H stretching vibration peaks disappeared. In contrast, for ISO-NU-1000, formate characteristic peaks persist. In the second set of experiments, the samples were digested after three water absorption cycles; neither material showed significant changes in formate amount (fig. 10, fig. 11). However, after immersing the sample in water and refreshing the water 5 times within 5 hours, the formate content in NU-1000 was significantly reduced (FIG. 12), but ISO-NU-1000 retained two formate groups per node (FIG. 13), which is comparable to that in the same nodecThe initial formate content of the pore region was consistent.
ISO-NU-1000cThe aperture window is small, the small window being such that it is at ISO-NU-000 relative to NU-1000cFormate ligands at the pore sites are difficult to replace by hydroxyl and water ligands; hydrogen bonding between water molecules in the channel and the MOF node is weakened, capillary forces are weakened, and pore collapse of ISO-NU-1000 during desorption of water can be suppressed when the node may be present with difficulty replacing formate ligands.
FIGS. 14, 15 and 16 show SEM images, N, of NU-1000, respectively 2 Isothermal and PXRD patterns, demonstrating the effect of pore collapse on morphology, porosity and crystallinity due to desorption of water, it can be seen that ISO-NU-1000 completely inhibits this behavior, cloggingcThe pores allow the zirconium-based MOF to exhibit excellent water adsorption cycle stability.
Claims (6)
1. A mesoporous zirconium-based metal organic framework compound is characterized in that the general formula is C 92 H 36 O 32 M 6 M represents metal Zr, the mesoporous zirconium-based metal organic framework compound takes 1,2,6, 7-tetra (4-carboxybenzene) pyrene as a ligand, and all carboxylic acid groups in the ligand participate in coordination to form M with M metal ions 6 (μ 3 -O) 4 (μ 3 -OH) 4 (HCOO) 4 The metal cluster has skeleton structure of one-dimensional mesoporous pore canalcsqA topology-type three-dimensional network structure;
the mesoporous zirconium-based metal organic framework compound has the lattice characteristics of a hexagonal system, and the space group isP6/mmm；
The unit cell parameters of the mesoporous zirconium-based metal organic framework compound are as followsa = b = 45.6079 Å，c = 13.0998 Å，α = β = 90°，γ = 120°；
Edge of the framecThe axial direction comprises a one-dimensional hexagonal mesoporous duct with the diameter of 3.2nm and a triangular microporous duct with the diameter of 1.2 nm; and windows of 0.64×0.08nm and 0.90×0.24nm in size are also present between the hexagonal cells and the triangular cells.
2. The method for synthesizing the mesoporous zirconium-based metal organic framework compound as claimed in claim 1, comprising the following steps:
step (1): dissolving M metal salt in an organic solvent, adding formic acid to dissolve completely and preheating;
step (2): adding ligand 1,2,6, 7-tetra (4-carboxybenzene) pyrene into an organic solvent, and dissolving after preheating;
step (3): mixing the solutions obtained in the step (1) and the step (2), adding formic acid again, then carrying out solvothermal reaction, and cooling after finishing to obtain pale yellow powder crystals;
step (4): finally, washing and drying to obtain a metal organic framework;
the organic solvent is N, N-dimethylformamide; the M metal salt is zirconium oxychloride octahydrate;
in the step (1), the dosage ratio of the zirconium oxychloride octahydrate to the organic solvent and the formic acid is 25 milligrams: 1-3 milliliters: 100-400 microliters;
the preheating temperature is 70-90 ℃ and the preheating time is 1-2 hours;
the molar ratio of ligand 1,2,6, 7-tetra (4-carboxylbenzenepyrene) to M metal salt is 1: 3-9.
3. The method for synthesizing a mesoporous zirconium-based metal organic framework compound according to claim 2, wherein the dosage ratio of ligand 1,2,6, 7-tetra (4-carboxylbenzenepyrene) to organic solvent in step (2) is 10 mg: 1-3 milliliters;
in the step (2), the preheating temperature is 70-90 ℃ and the preheating time is 1-2 hours.
4. The method for synthesizing a mesoporous zirconium-based metal organic framework compound according to claim 2, wherein the formic acid used in the step (3) is 100 to 300 microliters.
5. The method for synthesizing a mesoporous zirconium-based metal organic framework compound according to claim 2, wherein in the step (3), the solvothermal reaction temperature is 110-130 ℃ and the reaction time is 1-2 days.
6. Use of the mesoporous zirconium-based metal organic framework compound of claim 1 in a water vapor adsorption/desorption process or a thermal conversion system based on water adsorption principles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310076055.XA CN115975211B (en) | 2023-01-18 | 2023-01-18 | Mesoporous zirconium-based metal organic framework with high water stability, and synthetic method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310076055.XA CN115975211B (en) | 2023-01-18 | 2023-01-18 | Mesoporous zirconium-based metal organic framework with high water stability, and synthetic method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115975211A CN115975211A (en) | 2023-04-18 |
| CN115975211B true CN115975211B (en) | 2023-08-18 |
Family
ID=85959681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310076055.XA Active CN115975211B (en) | 2023-01-18 | 2023-01-18 | Mesoporous zirconium-based metal organic framework with high water stability, and synthetic method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115975211B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110790944A (en) * | 2019-11-14 | 2020-02-14 | 中国人民解放军国防科技大学 | Method for preparing zirconium metal organic framework nanotube |
| CN115197435A (en) * | 2021-04-09 | 2022-10-18 | 天津师范大学 | Polyion liquid @ metal organic framework composite material and removal method thereof 99 Application of Tc nuclide |
-
2023
- 2023-01-18 CN CN202310076055.XA patent/CN115975211B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110790944A (en) * | 2019-11-14 | 2020-02-14 | 中国人民解放军国防科技大学 | Method for preparing zirconium metal organic framework nanotube |
| CN115197435A (en) * | 2021-04-09 | 2022-10-18 | 天津师范大学 | Polyion liquid @ metal organic framework composite material and removal method thereof 99 Application of Tc nuclide |
Non-Patent Citations (1)
| Title |
|---|
| Zhiyong Lu et al.."Isomer of linker for NU-1000 yields a new she-type, catalytic, and hierarchically porous, Zr-based metal–organic framework".《Chem. Commun.》.2021,第57卷第3571-3574页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115975211A (en) | 2023-04-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | High efficiency synthesis of HKUST-1 under mild conditions with high BET surface area and CO2 uptake capacity | |
| Duan et al. | Ultrafast room-temperature synthesis of hierarchically porous metal–organic frameworks by a versatile cooperative template strategy | |
| Xiao et al. | Chemically blockable transformation and ultraselective low-pressure gas adsorption in a non-porous metal organic framework | |
| JP5453101B2 (en) | Porous organic / inorganic hybrid and adsorbent containing the same | |
| KR102267930B1 (en) | Novel aluminum-based metal-organic framework having a 3-dimensinal porous structure comprising 2 or more ligands, and preparation method therefor and uses thereof | |
| CN102030767B (en) | Supramolecular metal-organic framework (MOF) compound material | |
| Cheng et al. | Bimetallic metal-organic frameworks nanocages as multi-functional fillers for water-selective membranes | |
| WO2022088517A1 (en) | Bifunctional metal-organic framework film material, preparation method therefor and application thereof | |
| CN104193768A (en) | Small and medium dual-hole HKUST-1 material and preparation method and application thereof | |
| Liu et al. | Preparation and characterization of a hydrophobic metal–organic framework membrane supported on a thin porous metal sheet | |
| BR112021010139A2 (en) | Metal-organic structure, method and system for capturing water, and method for using the metal-organic structure | |
| CN104128163A (en) | Preparation method of microporous-mesoporous MIL-101 material and application thereof | |
| CN113667136B (en) | Ultrahigh-stability and low-cost metal-organic framework material for efficiently separating acetylene/carbon dioxide and preparation method thereof | |
| CN111187417A (en) | Modification method and application of metal organic framework material | |
| CN108707238B (en) | Metal organic framework material Co-PTTIC-TPB and synthetic method and application thereof | |
| CN111253582A (en) | Zirconium-based metal organic framework material, preparation method and application | |
| CN105693506A (en) | Synthesis method of porous titanium crystal metal organic framework material | |
| CN111375385A (en) | Preparation method and application of bimetallic organic framework adsorbent | |
| Schoedel et al. | Why design matters: From decorated metal-oxide clusters to functional metal-organic frameworks | |
| CN110540655A (en) | Method for preparing ZIF-L particles by using freezing technology | |
| Thomas et al. | Processing of thermally stable 3D hierarchical ZIF-8@ ZnO structures and their CO2 adsorption studies | |
| Pang et al. | Vacancies in metal− organic frameworks: formation, arrangement, and functions | |
| Cho et al. | Hydrothermal Green Synthesis of a Robust Al Metal-Organic-Framework Effective for Water Adsorption Heat Allocations | |
| Yu et al. | Seed assisted synthesis of an anionic metal–organic framework membrane for selective and permeable hydrogen separation | |
| CN115975211B (en) | Mesoporous zirconium-based metal organic framework with high water stability, and synthetic method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |