CN115304776B - Repairing method of metal organic framework material - Google Patents
Repairing method of metal organic framework material Download PDFInfo
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- CN115304776B CN115304776B CN202110494132.4A CN202110494132A CN115304776B CN 115304776 B CN115304776 B CN 115304776B CN 202110494132 A CN202110494132 A CN 202110494132A CN 115304776 B CN115304776 B CN 115304776B
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- 239000000463 material Substances 0.000 title claims abstract description 114
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000012670 alkaline solution Substances 0.000 claims abstract description 10
- 239000003929 acidic solution Substances 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 37
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 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
- 229910052751 metal Inorganic materials 0.000 claims description 11
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 10
- 239000013110 organic ligand Substances 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- 238000009396 hybridization Methods 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 239000002253 acid Substances 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 7
- 239000013084 copper-based metal-organic framework Substances 0.000 description 43
- 238000001035 drying Methods 0.000 description 20
- 239000011148 porous material Substances 0.000 description 14
- 239000012265 solid product Substances 0.000 description 13
- 238000001179 sorption measurement Methods 0.000 description 10
- 238000009210 therapy by ultrasound Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000013148 Cu-BTC MOF Substances 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011020 pilot scale process Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 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
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
-
- 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]
-
- 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
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Abstract
The invention provides a repair method of a metal organic framework material, which comprises the following steps: (1) Adding the metal organic framework material with collapsed structure into an acidic 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 in a stirring state to obtain the repaired metal-organic framework material. The method can effectively repair the collapsed metal organic framework material, is simple and easy to operate, and has excellent performance after repair.
Description
Technical Field
The invention relates to the field of metal organic framework materials, in particular to a repairing method of a metal organic framework material.
Background
Metal-organic framework (Metal-Organic Frameworks, MOF), also known as Metal coordination polymer, is a cubic network structure crystal formed by hybridization of inorganic Metal centers and organic ligands through coordination bonds, and is a family of microporous/mesoporous materials which are emerging in recent years. The MOF has the advantages of large specific surface area, developed pore structure, good stability, adjustable pore canal, capability of performing chemical modification according to target requirements, and the like, so that the MOF has wide application prospects in various fields of gas storage, gas adsorption separation, selectivity, chiral catalysts and the like.
However, until now, other research teams have not seen pilot scale up or industrial scale application of MOF materials, except for pilot scale up of Cu-based-metal organic framework (Cu-MOF) materials by BASF corporation in germany. Key to impeding the commercial application of MOF materials is their poor hydrothermal stability. In the practical use process, the MOF is extremely easy to be attacked by water molecules in the environment, so that coordination bonds are broken, and a framework structure is damaged.
The disposal of the invalid MOF material is a problem to be solved, the invalid MOF material mainly comprises metal compounds and aromatic compounds, the recycling of the substances is difficult, and part of the substances are toxic and harmful to the health of human bodies, such as bad treatment, and secondary pollution to the environment can be caused. Therefore, effective regeneration of spent MOF materials is of great interest.
Majano et al (G.Majano, et al, solvent-Mediated Reconstruction of the Metal-Organic Framework HKUST-1 (Cu) 3 (BTC) 2 ) Advanced Functional Materials, 2014, 24, 3855-3865) repairing the collapsed HKUST-1 porous metal-organic framework material by a solution soaking method, namely soaking and stirring for 1h by ethanol, and recovering the BET specific surface area of the material to 56% of that of the new HKUST-1 material after drying.
CN104592255a discloses a method for repairing a copper-based-metal organic framework porous material. The method comprises the steps of putting a copper-based-metal organic framework porous material with collapsed structure into a ball mill, and adding a repairing solvent for ball milling; and 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, and the adsorption capacity of the porous material can be recovered to 92% of that of the new HKUST-1 material. The method is efficient and green, but the MOF material has a lot of changes in performance under the action of ball milling mechanical force, such as size reduction of crystals, formation of defects on the surfaces of the crystals, change of the overall structure of the crystals and the like, and the changes affect the structural stability of the MOF material.
CN111410750a discloses a method for repairing Co-MOF-71 metal organic framework. The method takes 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: 0.1-1: 0.4, using N, N-dimethylformamide containing ethanol as a solvent, and recovering the collapsed Co-MOF-71 metal organic framework to a form consistent with XRD characteristic peaks of fresh Co-MOF-71 materials through solvothermal treatment. The repairing method is simple, a large amount of expensive organic ligands are needed 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 Co-MOF-71 material are not required, and the specific surface area and pore volume recovery condition is critical to the performance of the adsorption material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a repairing method of a metal organic framework material, which can effectively repair the metal organic framework material with collapsed structure, is simple and easy to operate, and has excellent performance after repairing.
The invention provides a repair method of a metal organic framework material, which comprises the following steps:
(1) Uniformly mixing the metal organic framework material with 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 in 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 hybridization of an oxygen-containing organic ligand of aromatic acid and 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 one or more of 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 preferred are terephthalic acid and/or trimesic acid; the derivative refers to the carboxylic acid ligand compound in which one or more carboxylic acid functional groups are replaced by functional groups such as 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, preferably copper.
Further, in the step (1), the acidic solution is one or more of hydrochloric acid solution, nitric acid solution, sulfuric acid solution, acetic acid solution and citric acid solution. The concentration of the acidic solution is 0.1-1.5 mol/L. The ratio of the addition amount of the acid solution to the metal organic framework material with collapsed structure is 3-10 mL/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-diethyl acetamide; preferably one or more of N, N-dimethylformamide, ethanol and isopropanol; more preferably N, N-dimethylformamide. The ratio of the addition amount of the organic solvent to the metal organic framework material with collapsed structure is 10-20 mL/g.
Further, in the step (2), the alkaline solution is one or more of sodium hydroxide solution, potassium hydroxide solution and sodium carbonate solution, and the concentration of the alkaline solution is 0.1-1.5 mol/L. The amount of the alkaline solution is enough to enable the pH value of the reaction system to be 2-5.
Further, in the step (2), the reaction temperature is 25-150 ℃, and the reaction time is 3-12 hours.
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 adopts one or two of ethanol, deionized water and N, N-dimethylformamide. The drying temperature is 80-200 ℃, and the drying time is 6-24 hours.
Further, in the step (1), the mixing is preferably carried out by adopting an ultrasonic treatment method, the ultrasonic power is 150-300W, and the time is 10-60 min.
Further, in the step (2), the stirring may be performed by using a technique conventionally used in the art. For example, mechanical stirring or magnetic stirring can be 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, purification and the like.
Further, the metal organic framework material with collapsed structure can be metal organic framework material which is destroyed in all framework structures in the field and can not meet the requirement of process adsorption performance, and is generally obtained by naturally storing fresh metal organic framework material obtained by adopting 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, is strong in operability and is suitable for large-scale production. The invention promotes the metal center and the organic ligand to carry out complexation 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 crystal size is not greatly different from that of the fresh metal organic framework material, the specific surface area and the pore volume can be basically restored to the level equivalent to that of the fresh metal organic framework material, and the crystal structure of the metal organic framework material is restored to the maximum extent.
Drawings
FIG. 1 is an X-ray diffraction pattern of fresh Cu-MOF materials and samples A-G of examples 1-5 and comparative example 1;
FIG. 2 is a scanning electron microscope image of fresh Cu-MOF material;
FIG. 3 is a scanning electron microscope image of sample B of example 1.
Detailed Description
The following examples further illustrate the repair method of the metal-organic framework material according to the present invention, but the scope of protection of the present invention is not limited to the following examples.
In the present invention, SEM was measured by using a 7500F cold field emission electron microscope manufactured by japan electronics corporation, and the microscopic morphology of the crystal was observed on the micrometer and nanometer scales. XRD was measured using a D/max2500 type X-ray diffractometer manufactured by Japanese Physics company under the following 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 material: 10.5g of copper nitrate trihydrate and 5.04g of trimesic acid are dissolved in 250mL of N, N-dimethylformamide, the mixture is stirred for 30min at room temperature, the obtained material is transferred into a stainless steel reaction kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, and then transferred into a drying oven to be subjected to standing reaction for 24h at 75 ℃. And (3) carrying out solid-liquid separation on the reaction solution, washing a solid product with absolute ethyl alcohol for three times, and then placing the solid product into a drying oven to be dried at the constant temperature of 150 ℃ for 24 hours, thus obtaining the fresh Cu-MOF material, wherein a scanning electron microscope image is shown in figure 2.
(2) Naturally placing the Cu-MOF material prepared in the step (1) for 1 month in a room temperature environment to obtain the Cu-MOF material with collapsed structure, and marking the Cu-MOF material as a sample A.
(3) 1g of Cu-MOF material sample A with collapsed structure is weighed and added into 10mL of 1mol/L hydrochloric acid solution, ultrasonic treatment is carried out for 10min at 300w power, and then 20mL of absolute ethyl alcohol is added for continuous ultrasonic treatment for 20min, so as to obtain a material A.
(4) Adding 1mol/L sodium hydroxide solution into the material A, regulating the pH value of a reaction system to 4, stirring the solution at the speed of 250rpm for reaction for 6 hours at 70 ℃, filtering the obtained material, washing the solid product with absolute ethyl alcohol for three times, and then placing the solid product into a drying oven for constant temperature drying at the temperature of 100 ℃ for 24 hours to obtain a repaired Cu-MOF material, wherein the repaired Cu-MOF material is marked as a sample B, and a scanning electron microscope image is shown in figure 3.
Example 2
(1) 1g of the Cu-MOF material sample A with collapsed structure prepared in the example 1 is weighed, added into 10mL of 0.3mol/L hydrochloric acid solution, and after ultrasonic treatment for 10min at 200w power, 10mL of N, N-dimethylformamide is added for continuous ultrasonic treatment for 20min, so as to prepare a material A.
(2) Adding 0.1mol/L sodium hydroxide solution into the material A, regulating the pH value of a reaction system to be 3, stirring the solution at the speed of 250rpm at 80 ℃ for reaction for 12 hours, filtering the obtained material, washing a solid product with absolute ethyl alcohol for three times, and then placing the solid product into a drying box for constant temperature drying at 150 ℃ for 24 hours to obtain the repaired Cu-MOF material, which is marked as a sample C.
Example 3
(1) 1g of Cu-MOF material sample A with collapsed structure prepared in example 1 is weighed, added into 5mL of 0.5mol/L hydrochloric acid solution, and subjected to ultrasonic treatment for 10min at 300w power, and then 15mL of absolute ethyl alcohol is added for continuous ultrasonic treatment for 20min, so as to prepare a material A.
(2) Adding 0.5mol/L sodium hydroxide solution into the material A, regulating the pH value of a reaction system to be 4, stirring the solution at the speed of 300rpm at 60 ℃ for reaction for 3 hours, filtering the obtained material, washing a solid product with absolute ethyl alcohol for three times, and then placing the solid product into a drying box for drying at the constant temperature of 100 ℃ for 24 hours to obtain the repaired Cu-MOF material, which is marked as a sample D.
Example 4
(1) 1g of the Cu-MOF material sample A with collapsed structure prepared in the example 1 is weighed, added into 7mL of 0.8mol/L hydrochloric acid solution, and after ultrasonic treatment is carried out for 10min at the power of 200w, 15mL of N, N-dimethylformamide is added for continuous ultrasonic treatment for 20min, so as to prepare a material A.
(2) Adding 0.5mol/L sodium hydroxide solution into the material A, regulating the pH value of a reaction system to 2, stirring the solution at the speed of 300rpm at 45 ℃ for reaction for 8 hours, filtering the obtained material, washing a solid product with absolute ethyl alcohol for three times, and then placing the solid product into a drying box for drying at the constant temperature of 100 ℃ for 24 hours to obtain the repaired Cu-MOF material, which is marked as a sample E.
Example 5
(1) 1g of the Cu-MOF material sample A with collapsed structure prepared in the example 1 is weighed, added into 3mL of 1.4mol/L hydrochloric acid solution, ultrasonic is carried out for 10min at 300w power, 17mL of absolute ethyl alcohol is added, and ultrasonic is continued for 20min, so as to prepare a material A.
(2) Adding 0.8mol/L sodium hydroxide solution into the material A, regulating the pH value of a reaction system to be 3, stirring the solution at the speed of 300rpm for reaction for 10 hours at the temperature of 30 ℃, filtering the obtained material, washing the solid product with absolute ethyl alcohol for three times, and then placing the solid product into a drying box for drying at the constant temperature of 100 ℃ for 24 hours to obtain the repaired Cu-MOF material, which is marked as a sample F.
Comparative example 1
1G of the Cu-MOF material sample A with collapsed structure prepared in example 1 is weighed and added into 20mL of N, N-dimethylformamide, after ultrasonic treatment is carried out for 10min at 300w, the solution is stirred at the speed of 250rpm for reaction for 12h at 80 ℃, then the obtained material is filtered, the solid product is washed three times by absolute ethyl alcohol and then is put into a drying box for drying at the constant temperature of 100 ℃ for 24h, and the repaired Cu-MOF material is obtained and is marked as a sample G.
Comparative example 2
The difference compared to example 1 is only that 1mL of 1mol/L hydrochloric acid solution is used in step (3). The repaired Cu-MOF material was obtained and designated as sample H.
Comparative example 3
The difference compared to example 1 is only that step (3) uses 14mL of 1mol/L hydrochloric acid solution. The repaired Cu-MOF material was obtained and designated as sample I.
Comparative example 4
The difference compared with example 1 is that in step (4), 1mol/L sodium hydroxide solution was added to the material A, and the pH of the reaction system was adjusted to 6.5. The repaired Cu-MOF material was obtained and designated as sample J.
Test example 1
Pore structure parameters were determined for all examples and comparative examples, and the specific results are shown in table 1. The BET specific surface area and pore volume were measured by low temperature liquid nitrogen adsorption, and the test instrument was ASAP 2020 type adsorbent from Micromeritics company of America. The relative crystallinity was calculated by setting the crystallinity to 100% based on the fresh Cu-MOF material prepared in example 1, and the crystallinity was measured by X-ray diffraction method. The adsorption performance of the sample on methane was tested by using a high pressure gas adsorber of American microphone company HPVA-100, the sample was degassed in the apparatus at 200℃for 12 hours before the test, and the test conditions for the methane adsorption amount in Table 1 were 25℃and 3.5MPa.
TABLE 1 physicochemical parameters and adsorption Properties of the materials obtained in examples and comparative examples
| Sample of | BET specific surface area (m) 2 /g） | Pore volume (cm) 3 /g) | Relative crystallinity (%) | Methane adsorption amount/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, samples B-F of Cu-MOF materials repaired by the repair method of the present invention can be restored to substantially comparable levels for fresh Cu-MOF materials in terms of specific surface area and pore volume. 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 matched with that of a fresh Cu-MOF material, the characteristic peak strength is slightly reduced, but the relative crystallinity of the repaired Cu-MOF material sample B-F can reach 98% of that of the fresh Cu-MOF material; in sample G of comparative example 1, although the characteristic peak of the Cu-MOF material was also detected, the repairing effect was limited, and the BET specific surface area was recovered to only 51% of that of the fresh Cu-MOF material.
As can be seen from fig. 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 greatly changed, and the crystal surface is smooth, and the original octahedral structure of the crystal is maintained, i.e., the crystal structure of the Cu-MOF material is recovered to the maximum extent.
Claims (11)
1. A repairing method of a metal organic framework material comprises the following steps:
(1) Uniformly mixing the metal organic framework material with collapsed structure with an acidic solution, adding an organic solvent, and uniformly mixing to obtain a material A;
(2) Adding an alkaline solution into the material A, and reacting in a stirring state to obtain a repaired metal-organic framework material;
the metal organic framework material is a three-dimensional network structure crystal formed by hybridization of an oxygen-containing organic ligand of aromatic acid and an inorganic metal center through a coordination bond;
the ratio of the addition amount of the acid solution to the metal organic framework material with collapsed structure is 3-10 mL/g;
the amount of the alkaline solution is enough to enable the pH value of the reaction system to be 2-5.
2. A method according to claim 1, characterized in that: the oxygen-containing organic ligand of the aromatic acid is one or more of bidentate and tridentate carboxylic acid ligand compounds and derivatives thereof; 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, and cyano groups.
3. A method according to claim 2, characterized in that: the oxygen-containing organic ligand of the aromatic acid is one or more of terephthalic acid, isophthalic acid, trimesic acid, 1, 4-naphthalene dicarboxylic acid, 1, 5-naphthalene dicarboxylic acid and 2, 6-naphthalene dicarboxylic acid.
4. A method according to claim 2, characterized in that: the oxygen-containing organic ligand of the aromatic acid is terephthalic acid and/or trimesic acid.
5. A method according to claim 1, characterized in that: the metal in the inorganic metal center is one or more of copper, iron, zirconium, zinc, magnesium, aluminum, cobalt, chromium, nickel, calcium or titanium.
6. The method according to claim 5, wherein: the metal in the inorganic metal center is copper.
7. A method according to claim 1, characterized in that: in the step (1), the acidic solution is one or more of hydrochloric acid solution, nitric acid solution, sulfuric acid solution, acetic acid solution and citric acid solution; the concentration of the acidic solution is 0.1-1.5 mol/L.
8. A method according to claim 1, characterized in that: in the step (1), the organic solvent is one or more of methanol, ethanol, isopropanol, ethylene glycol, isobutanol, glycerol, N-dimethylformamide and N, N-diethyl acetamide; the ratio of the addition amount of the organic solvent to the metal organic framework material with collapsed structure is 10-20 mL/g.
9. The method according to claim 8, wherein: in the step (1), the organic solvent is one or more of N, N-dimethylformamide, ethanol and isopropanol.
10. A method according to claim 1, characterized in that: in the step (2), the alkaline solution is one or more of sodium hydroxide solution, potassium hydroxide solution and sodium carbonate solution, and the concentration of the alkaline solution is 0.1-1.5 mol/L.
11. A method according to claim 1, characterized in that: in the step (2), the reaction temperature is 25-150 ℃ and the reaction time is 3-12 h.
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