CN115304776A - Method for repairing metal organic framework material - Google Patents
Method for repairing metal organic framework material Download PDFInfo
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- CN115304776A CN115304776A CN202110494132.4A CN202110494132A CN115304776A CN 115304776 A CN115304776 A CN 115304776A CN 202110494132 A CN202110494132 A CN 202110494132A CN 115304776 A CN115304776 A CN 115304776A
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- 239000000463 material Substances 0.000 title claims abstract description 120
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000000243 solution Substances 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000012670 alkaline solution Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000013078 crystal Substances 0.000 claims description 13
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
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- 229910052751 metal Inorganic materials 0.000 claims description 9
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- 239000003929 acidic solution Substances 0.000 claims description 7
- 239000013110 organic ligand Substances 0.000 claims description 7
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- 239000003446 ligand Substances 0.000 claims description 5
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- 239000010949 copper Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 claims description 2
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 claims description 2
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 claims description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 230000008439 repair process Effects 0.000 abstract description 2
- 239000013084 copper-based metal-organic framework Substances 0.000 description 47
- 238000001035 drying Methods 0.000 description 19
- 239000012265 solid product Substances 0.000 description 14
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000013148 Cu-BTC MOF Substances 0.000 description 5
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- 239000013256 coordination polymer Substances 0.000 description 1
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- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
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- 239000013335 mesoporous material Substances 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7022—Aliphatic hydrocarbons
- B01D2257/7025—Methane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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Abstract
The invention provides a method for repairing a metal organic framework material, which comprises the following steps: (1) Adding the metal organic framework material with the collapsed structure into an acid solution, uniformly mixing, adding an organic solvent, and uniformly mixing to obtain a material A; (2) And adding an alkaline solution into the material A, and reacting under a stirring state to obtain the repaired metal organic framework material. The method can effectively repair the metal organic framework material with the collapsed structure, is simple and easy to operate, and the repaired metal organic framework material has excellent performance.
Description
Technical Field
The invention relates to the field of metal organic framework materials, in particular to a method for repairing a metal organic framework material.
Background
Metal-Organic Frameworks (MOFs), also known as Metal coordination polymers, are cubic network crystals formed by hybridization of inorganic Metal centers and Organic ligands through coordination bonds, and are a family of microporous/mesoporous materials emerging in recent years. The MOF has the advantages of large specific surface area, developed pore structure, good stability, adjustable pore channels, chemical modification according to target requirements and the like, so the MOF has wide application prospects in the fields of gas storage, gas adsorption and separation, selectivity, chiral catalysts and the like.
However, to date, no pilot scale or industrial scale application of MOF materials has been reported by other research teams, except for the pilot scale of Cu-based-metal organic framework (Cu-MOF) materials by BASF, germany. The key to hindering the industrial application of MOF materials is their poor hydrothermal stability. In the actual use process, the MOF is very easy to be attacked by water molecules in the environment, so that the coordination bonds are broken, and the framework structure is damaged.
The disposal of the waste MOF material is an urgent problem to be solved, the waste MOF material mainly comprises metal compounds and aromatic compounds, the recovery of the substances is difficult, and part of the components are toxic, so that the health of human bodies is harmed, for example, the disposal is not good, and secondary pollution to the environment is caused. Therefore, there is considerable interest in effectively recycling spent MOF materials.
G.Majano et al (G.Majano, et al, solvent-medial Reconnection of the Metal-Organic Framework HKUST-1 (Cu) 3 (BTC) 2 ) Advanced Functional Materials, 2014, 24, 3855-3865) repairing collapsed HKUST-1 porous metal organic framework Materials by adopting a solution soaking method, namely soaking and stirring for 1h by adopting ethanol, and recovering the BET specific surface area of the Materials to 56% of that of new HKUST-1 Materials after drying.
CN104592255A discloses a method for repairing a copper-based-metal organic framework porous material. Putting the copper-based-metal organic framework porous material with the collapsed structure into a ball mill, and adding a repairing solvent for ball milling; and (4) taking out the solid material after ball milling and drying to obtain the repaired copper-based-metal organic framework porous material. The BET specific surface area of the copper-based-metal organic framework porous material repaired by the method can be recovered to 95% of that of a new HKUST-1 material at most, and the adsorption capacity of the copper-based-metal organic framework porous material can be recovered to 92% of that of the new HKUST-1 material at most. The method is efficient and green, but the properties of the MOF material can be changed greatly under the action of the ball milling mechanical force, such as the reduction of the size of crystals, the formation of defects on the surfaces of the crystals, the change of the overall structure of the crystals and the like, and the changes can influence the structural stability of the MOF material.
CN111410750A discloses a method for repairing a Co-MOF-71 metal organic framework. The method takes a collapsed Co-MOF-71 metal organic framework as a starting material, takes ligand terephthalic acid for synthesizing the Co-MOF-71 metal organic framework as a repairing agent, and preferably, the mass ratio of the collapsed Co-MOF-71 material to the repairing agent terephthalic acid is 1:0.1 to 1: and 0.4, taking N, N-dimethylformamide containing ethanol as a solvent, and recovering the collapsed Co-MOF-71 metal-organic framework to a shape consistent with the XRD characteristic peak of the fresh Co-MOF-71 material through solvent heat treatment. The repairing method is simple, but a large amount of expensive organic ligands need to be added, and the repaired Co-MOF-71 material is pyrolyzed to be used as a precursor of a Co-based catalyst for catalyzing the conversion of synthesis gas, so that the specific surface area and pore volume recovery condition of the material are not required, and the material is of great importance for the performance of the adsorbing material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for repairing a metal-organic framework material, the method can be used for effectively repairing the metal-organic framework material with a collapsed structure, the method is simple and easy to operate, and the repaired metal-organic framework material has excellent performance.
The invention provides a method for repairing a metal organic framework material, which comprises the following steps:
(1) Uniformly mixing the metal organic framework material with the collapsed structure with an acidic solution, adding an organic solvent, and uniformly mixing to obtain a material A;
(2) And adding an alkaline solution into the material A, and reacting under a stirring state to obtain the repaired metal organic framework material.
Further, the metal-organic framework material refers to a three-dimensional network structure crystal formed by hybridizing an oxygen-containing organic ligand of an aromatic acid with an inorganic metal center through a coordination bond.
Further, the oxygen-containing organic ligand of the aromatic acid is one or more of bidentate and tridentate carboxylic acid ligand compounds and derivatives thereof; preferably terephthalic acid, isophthalic acid, trimesic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid and the like; further preferably terephthalic acid and/or trimesic acid; the derivatives refer to carboxylic acid ligand compounds in which one or more carboxylic acid functional groups are substituted with nitro groups, hydroxyl groups, methyl groups, cyano groups, and the like.
Further, the metal in the inorganic metal center is one or more of copper, iron, zirconium, zinc, magnesium, aluminum, cobalt, chromium, nickel, calcium or titanium, and is preferably copper.
Further, in the step (1), the acidic solution is one or more of a hydrochloric acid solution, a nitric acid solution, a sulfuric acid solution, an acetic acid solution and a citric acid solution. The concentration of the acidic solution is 0.1 to 1.5mol/L. The ratio of the addition amount of the acid solution to the metal-organic framework material with the collapsed structure is 3-10mL/g.
Further, in the step (1), the organic solvent is one or more of methanol, ethanol, isopropanol, ethylene glycol, isobutanol, glycerol, N-dimethylformamide and N, N-diethylacetamide; preferably one or more of N, N-dimethylformamide, ethanol and isopropanol; more preferably N, N-dimethylformamide. The proportion of the addition amount of the organic solvent to the metal-organic framework material with the collapsed structure is 10-20mL/g.
Further, in the step (2), the alkaline solution is one or more of a sodium hydroxide solution, a potassium hydroxide solution and a sodium carbonate solution, and the concentration of the alkaline solution is 0.1 to 1.5mol/L. The amount of the alkaline solution added was such that the pH of the reaction system was 2~5.
In the step (2), the reaction temperature is 25 to 150 ℃, and the reaction time is 3 to 12h.
Further, in the step (2), the material obtained after the reaction is subjected to post-treatment to obtain the repaired metal organic framework material. Wherein the post-treatment comprises filtration, washing and drying.
Further, the filtration, washing and drying may employ techniques conventionally used in the art. For example, the detergent is one or two of ethanol, deionized water and N, N-dimethylformamide. The drying temperature is 80 to 200 ℃, and the drying time is 6 to 24h.
Furthermore, in the step (1), the mixing is preferably carried out by using an ultrasonic treatment method, wherein the ultrasonic power is 150-300W, and the time is 10-60 min.
Further, in the step (2), stirring may be carried out by a technique conventionally used in the art. If mechanical stirring or magnetic stirring is adopted, the stirring speed is 50-500 rpm, and the stirring time is 10-60 min.
Further, the repaired metal organic framework material obtained in the step (2) can be used for adsorption, separation and purification and the like.
Further, the metal-organic framework material with collapsed structure may be a metal-organic framework material in which all framework structures in the field are destroyed and cannot meet the requirements of process adsorption performance, and is generally obtained by naturally storing fresh metal-organic framework materials obtained by a conventional method in the field for several weeks or months.
Compared with the prior art, the invention has the following advantages:
the repairing method is simple and feasible, can be operated and is suitable for large-scale production. The invention promotes the metal center and the organic ligand to carry out complexing reaction again by strictly controlling the dosage of the acidic solution and the alkaline solution, thereby repairing the metal organic framework material.
The metal organic framework material repaired by the method has high crystallinity, the difference between the crystal size and the fresh metal organic framework material is not large, the specific surface area and the pore volume can be basically recovered to the level equivalent to the fresh metal organic framework material, and the crystal structure of the metal organic framework material is recovered to the maximum extent.
Drawings
FIG. 1 is an X-ray diffraction pattern of fresh Cu-MOF material and samples A-G from examples 1-5 and comparative example 1;
FIG. 2 is a scanning electron micrograph of fresh Cu-MOF material;
FIG. 3 is a scanning electron micrograph of sample B of example 1.
Detailed Description
The method for repairing a metal-organic framework material of the present invention will be further described with reference to the following examples, but the scope of the present invention is not limited to the following examples.
In the present invention, SEM measurement is carried out by observing the microscopic morphology of the crystal on a micrometer and nanometer scale using a 7500F type cold field emission electron microscope manufactured by Nippon electronics Co. XRD was measured by using X-ray diffractometer model D/max2500 manufactured by Japan science, under the following test conditions: the voltage is 40KV, the current is 80mA, a CuK alpha target is selected, and the incident wavelength is 0.15405 nm.
Example 1
(1) Preparation of fresh Cu-MOF materials: dissolving 10.5g of copper nitrate trihydrate and 5.04g of trimesic acid in 250mL of N, N-dimethylformamide, continuously stirring at room temperature for 30min, transferring the obtained material to a stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, transferring to a drying box, and standing at 75 ℃ for reaction for 24h. And (3) carrying out solid-liquid separation on the reaction solution, washing the solid product with absolute ethyl alcohol for three times, and then putting the solid product into a drying oven to dry for 24 hours at a constant temperature of 150 ℃ to obtain a fresh Cu-MOF material, wherein a scanning electron micrograph is shown in figure 2.
(2) And (3) naturally placing the Cu-MOF material prepared in the step (1) at room temperature for 1 month to obtain the Cu-MOF material with the collapsed structure, and marking as a sample A.
(3) Weighing 1g of Cu-MOF material sample A with collapsed structure, adding the sample A into 10mL of hydrochloric acid solution at a concentration of 1mol/L, carrying out ultrasonic treatment for 10min at a power of 300w, adding 20mL of absolute ethyl alcohol, and continuing the ultrasonic treatment for 20min to obtain a material A.
(4) Adding 1mol/L sodium hydroxide solution into the material A, adjusting the pH value of a reaction system to be 4, stirring the solution at the speed of 250rpm at 70 ℃ to react for 6h, filtering the obtained material, washing a solid product with absolute ethyl alcohol for three times, then placing the solid product into a drying oven to dry for 24h at the constant temperature of 100 ℃, thus obtaining a repaired Cu-MOF material, marking the repaired Cu-MOF material as a sample B, and obtaining a scanning electron microscope picture shown in figure 3.
Example 2
(1) 1g of the Cu-MOF material sample A with the collapsed structure prepared in example 1 was weighed, added to 10mL of 0.3mol/L hydrochloric acid solution, and subjected to ultrasonic processing at 200w for 10min, and then 10mL of N, N-dimethylformamide was added and ultrasonic processing was continued for 20min, thereby obtaining a material A.
(2) Adding 0.1mol/L sodium hydroxide solution into the material A, adjusting the pH value of a reaction system to be 3, stirring the solution at the speed of 250rpm at 80 ℃ to react for 12h, filtering the obtained material, washing a solid product with absolute ethyl alcohol for three times, and drying the solid product in a drying oven at the constant temperature of 150 ℃ for 24h to obtain a repaired Cu-MOF material, wherein the sample C is marked as the sample C.
Example 3
(1) Weighing 1g of the Cu-MOF material sample A with the collapsed structure prepared in the example 1, adding the sample A into 5mL of hydrochloric acid solution with the concentration of 0.5mol/L, carrying out ultrasonic treatment at the power of 300w for 10min, adding 15mL of absolute ethyl alcohol, and continuing the ultrasonic treatment for 20min to prepare a material A.
(2) Adding 0.5mol/L sodium hydroxide solution into the material A, adjusting the pH value of a reaction system to be 4, stirring the solution at the speed of 300rpm at 60 ℃ to react for 3h, filtering the obtained material, washing a solid product with absolute ethyl alcohol for three times, and drying the solid product in a drying oven at the constant temperature of 100 ℃ for 24h to obtain a repaired Cu-MOF material, wherein the repaired Cu-MOF material is marked as a sample D.
Example 4
(1) 1g of the Cu-MOF material sample A with the collapsed structure prepared in example 1 is weighed and added into 7mL of hydrochloric acid solution at the concentration of 0.8mol/L, ultrasonic treatment is carried out for 10min at the power of 200w, then 15mL of N, N-dimethylformamide is added for continuous ultrasonic treatment for 20min, and the material A is prepared.
(2) Adding 0.5mol/L sodium hydroxide solution into the material A, adjusting the pH value of a reaction system to 2, stirring the solution at the speed of 300rpm at 45 ℃ to react for 8h, filtering the obtained material, washing a solid product with absolute ethyl alcohol for three times, and drying the solid product in a drying oven at the constant temperature of 100 ℃ for 24h to obtain a repaired Cu-MOF material, wherein the repaired Cu-MOF material is marked as a sample E.
Example 5
(1) 1g of the Cu-MOF material sample A with the collapsed structure prepared in the example 1 is weighed and added into 3mL of hydrochloric acid solution with the concentration of 1.4mol/L, ultrasonic treatment is carried out for 10min at the power of 300w, 17mL of absolute ethyl alcohol is added, and the ultrasonic treatment is continued for 20min, so that a material A is prepared.
(2) Adding 0.8mol/L sodium hydroxide solution into the material A, adjusting the pH value of a reaction system to 3, stirring the solution at the speed of 300rpm at 30 ℃ to react for 10 hours, filtering the obtained material, washing a solid product with absolute ethyl alcohol for three times, and drying the solid product in a drying oven at the constant temperature of 100 ℃ for 24 hours to obtain a repaired Cu-MOF material, wherein the repaired Cu-MOF material is marked as a sample F.
Comparative example 1
Weighing 1G of the Cu-MOF material sample A with the collapsed structure prepared in the embodiment 1, adding the sample A into 20mL of N, N-dimethylformamide, carrying out ultrasonic treatment at the power of 300w for 10min, stirring the solution at the speed of 250rpm at 80 ℃ to react for 12h, filtering the obtained material, washing a solid product with absolute ethyl alcohol for three times, and drying the solid product in a drying oven at the constant temperature of 100 ℃ for 24h to obtain a repaired Cu-MOF material, wherein the repaired Cu-MOF material is marked as a sample G.
Comparative example 2
Compared with example 1, the difference is only that step (3) adopts 1mL,1mol/L hydrochloric acid solution. The repaired Cu-MOF material was obtained and designated as sample H.
Comparative example 3
Compared with example 1, the difference is only that step (3) adopts 14mL,1mol/L hydrochloric acid solution. The repaired Cu-MOF material is obtained and is marked as a sample I.
Comparative example 4
Compared with example 1, the difference is only that in step (4), 1mol/L sodium hydroxide solution is added into the material A, and the pH value of the reaction system is adjusted to 6.5. The repaired Cu-MOF material was obtained and designated sample J.
Test example 1
The pore structure parameters of all the samples of examples and comparative examples were determined and the specific results are shown in table 1. The BET specific surface area and the pore volume are measured by a low-temperature liquid nitrogen adsorption method, and an analyzer is an ASAP 2020 type adsorber manufactured by Micromeritics corporation in America. Relative crystallinity was calculated by setting the degree of crystallinity to 100% based on the fresh Cu-MOF material prepared in example 1, as determined by X-ray diffraction. The adsorption performance of the sample on methane was tested by using a HPVA-100 model high pressure gas adsorption apparatus from Michco USA, the sample was degassed at 200 deg.C for 12h in the apparatus before the test, and the test conditions for the methane adsorption amount in Table 1 were 25 deg.C and 3.5MPa.
TABLE 1 physicochemical parameters and adsorption Properties of the materials obtained in examples and comparative examples
| Sample (I) | BET specific surface area (m) 2 /g） | Pore volume (cm) 3 /g) | Relative crystallinity (%) | Methane adsorption/cm g -1 |
| Fresh Cu-MOF material | 1648 | 0.69 | 100 | 182 |
| Sample A | 95 | 0.10 | 8 | 16 |
| Sample B | 1567 | 0.65 | 95 | 173 |
| Sample C | 1586 | 0.67 | 98 | 175 |
| Sample D | 1483 | 0.61 | 90 | 165 |
| Sample E | 1506 | 0.62 | 91 | 167 |
| Sample F | 1534 | 0.63 | 93 | 169 |
| Sample G | 846 | 0.48 | 43 | 77 |
| Sample H | 945 | 0.50 | 51 | 86 |
| Sample I | 823 | 0.46 | 42 | 71 |
| Sample J | 751 | 0.44 | 40 | 62 |
As can be seen from Table 1, the specific surface area and pore volume of the Cu-MOF material samples B-F repaired by the repair method of the present invention can be substantially restored to the equivalent levels of the fresh Cu-MOF material. As can be seen from Table 1 and FIG. 1, the XRD peak intensity of the collapsed Cu-MOF material is very weak; the XRD characteristic peak position of the repaired Cu-MOF material sample B-F is almost completely consistent with that of the fresh Cu-MOF material, the strength of the characteristic peak is slightly reduced, but the relative crystallinity of the repaired Cu-MOF material sample B-F can reach 98 percent of that of the fresh Cu-MOF material; sample G of comparative example 1, although a characteristic peak of Cu-MOF material was also detected, had a limited repairing effect and the BET specific surface area was restored to 51% of that of fresh Cu-MOF material.
As can be seen from FIGS. 2 and 3, compared with the fresh Cu-MOF material (FIG. 2), the crystal size of the repaired Cu-MOF material sample B (FIG. 3) is not changed much, the crystal surface is smooth, and the original octahedral structure of the crystal is still maintained, i.e. the crystal structure of the Cu-MOF material is recovered to the maximum extent.
Claims (10)
1. A method for repairing a metal organic framework material comprises the following steps:
(1) Uniformly mixing the metal organic framework material with the collapsed structure with an acidic solution, adding an organic solvent, and uniformly mixing to obtain a material A;
(2) And adding an alkaline solution into the material A, and reacting under a stirring state to obtain the repaired metal organic framework material.
2. The method of claim 1, wherein: the metal organic framework material is a three-dimensional network structure crystal formed by hybridizing an oxygen-containing organic ligand of aromatic acid with an inorganic metal center through a coordination bond.
3. The method of claim 2, wherein: the oxygen-containing organic ligand of the aromatic acid is one or more of bidentate and tridentate carboxylic acid ligand compounds and derivatives thereof; preferably terephthalic acid, isophthalic acid, trimesic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid and the like; further preferably terephthalic acid and/or trimesic acid; the derivative refers to carboxylic acid ligand compound in which one or more carboxylic acid functional groups are substituted by nitro group, hydroxyl group, methyl group, cyano group.
4. The method of claim 2, wherein: the metal in the inorganic metal center is one or more of copper, iron, zirconium, zinc, magnesium, aluminum, cobalt, chromium, nickel, calcium or titanium, and is preferably copper.
5. The method of claim 1, wherein: in the step (1), the acidic solution is one or more of a hydrochloric acid solution, a nitric acid solution, a sulfuric acid solution, an acetic acid solution and a citric acid solution; the concentration of the acidic solution is 0.1 to 1.5mol/L.
6. The method of claim 1 or 5, wherein: the ratio of the addition amount of the acid solution to the metal-organic framework material with the collapsed structure is 3-10mL/g.
7. The method of claim 1, wherein: in the step (1), the organic solvent is one or more of methanol, ethanol, isopropanol, ethylene glycol, isobutanol, glycerol, N-dimethylformamide and N, N-diethylacetamide; preferably one or more of N, N-dimethylformamide, ethanol and isopropanol; the proportion of the addition amount of the organic solvent to the metal-organic framework material with the collapsed structure is 10-20mL/g.
8. The method of claim 1, wherein: in the step (2), the alkaline solution is one or more of a sodium hydroxide solution, a potassium hydroxide solution and a sodium carbonate solution, and the concentration of the alkaline solution is 0.1 to 1.5mol/L.
9. The method of claim 1 or 8, wherein: the amount of the alkaline solution added was such that the pH of the reaction system was 2~5.
10. The method of claim 1, wherein: in the step (2), the reaction temperature is 25 to 150 ℃, and the reaction time is 3 to 12h.
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