CN104338513A - Metal organic framework material, preparation method and application thereof - Google Patents
Metal organic framework material, preparation method and application thereof Download PDFInfo
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- CN104338513A CN104338513A CN201310428964.1A CN201310428964A CN104338513A CN 104338513 A CN104338513 A CN 104338513A CN 201310428964 A CN201310428964 A CN 201310428964A CN 104338513 A CN104338513 A CN 104338513A
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 154
- 239000000463 material Substances 0.000 title claims abstract description 153
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000007789 gas Substances 0.000 claims abstract description 21
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 52
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 26
- 239000001569 carbon dioxide Substances 0.000 claims description 26
- 159000000013 aluminium salts Chemical class 0.000 claims description 22
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000001228 spectrum Methods 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 9
- 238000001179 sorption measurement Methods 0.000 claims description 9
- SBBQDUFLZGOASY-OWOJBTEDSA-N 4-[(e)-2-(4-carboxyphenyl)ethenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1\C=C\C1=CC=C(C(O)=O)C=C1 SBBQDUFLZGOASY-OWOJBTEDSA-N 0.000 claims description 7
- 238000010304 firing Methods 0.000 claims description 5
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims description 4
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims description 3
- 241001580033 Imma Species 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- -1 N-DEF Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 6
- 239000003446 ligand Substances 0.000 abstract 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 24
- 229940125782 compound 2 Drugs 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- 229940125904 compound 1 Drugs 0.000 description 17
- 239000004411 aluminium Substances 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 229910052723 transition metal Inorganic materials 0.000 description 9
- 150000003624 transition metals Chemical class 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 239000004809 Teflon Substances 0.000 description 5
- 229920006362 Teflon® Polymers 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000013132 MOF-5 Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000013236 Zn4O(BTB)2 Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- UOFDVLCOMURSTA-UHFFFAOYSA-N 2-(2-carboxyphenoxy)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1OC1=CC=CC=C1C(O)=O UOFDVLCOMURSTA-UHFFFAOYSA-N 0.000 description 1
- SVAJWMFPXLZPHL-UHFFFAOYSA-N 2-[3,5-bis(2-carboxyphenyl)phenyl]benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC(C=2C(=CC=CC=2)C(O)=O)=CC(C=2C(=CC=CC=2)C(O)=O)=C1 SVAJWMFPXLZPHL-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- GVJZOZADGAKACR-UHFFFAOYSA-N O(C1=CC=C(C(=O)O)C=C1)C1=CC=C(C(=O)O)C=C1.O(C1=CC=C(C(=O)O)C=C1)C1=CC=C(C(=O)O)C=C1 Chemical group O(C1=CC=C(C(=O)O)C=C1)C1=CC=C(C(=O)O)C=C1.O(C1=CC=C(C(=O)O)C=C1)C1=CC=C(C(=O)O)C=C1 GVJZOZADGAKACR-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
-
- 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
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a metal organic framework material, a preparation method and application thereof. The metal organic framework material has a chemical formula of M (OH) (L). Wherein M is trivalent aluminum ion, L is 4, 4 '-diphenyl ether dicarboxylic acid or a gemini ligand of 4, 4' -diphenylethylene dicarboxylic acid. The method of preparing the metal organic framework material comprises blending a trivalent aluminum salt and a gemini ligand to form a solution, and heating the solution to prepare the metal organic framework material. Metal organic framework materials can be used to adsorb gases.
Description
Technical field
The invention relates to a kind of metal-organic framework materials, Its Preparation Method And Use, particularly a kind of metal-organic framework materials, Its Preparation Method And Use with trivalent aluminium ion and two bud dentate.
Background technology
Metal-organic framework materials (Metal-Organic Frameworks, MOFs) is the organic and inorganic coordination polymer developed rapidly in recent years.In general, metal-organic framework materials is formed by central metal and organic coordination base institute bond.Further, according to the stack manner of the central metal in metal-organic framework materials and organic coordination base, metal-organic framework materials also can distinguish the kind of one dimension, two dimension and three-dimensional arrangement further.
Metal-organic framework materials is a kind of porous material.In general, porous material, owing to having more hole, larger specific area, is thus often used in the fields such as gas absorption, gas separaion, catalysis, sensing element, particularly in carbon dioxide and the absorption of hydrogen and the field of storage.For example, porous material can be arranged on discharge place of carbon dioxide by user, uses absorbing carbon dioxide, to reduce the impact of carbon dioxide on environment.On the other hand, porous material also can be used as Recent Progress in Hydrogen Storage Materials, uses the mode replacing and store liquefaction hydrogen through steel cylinder.
Compared to the porous material of other kind, metal-organic framework materials has structure and changes various advantage.Therefore, user can adjust composition and the hole size of metal-organic framework materials according to its demand.In addition, on application, metal-organic framework materials has higher gas absorption amount when low pressure, and metal-organic framework materials also has the advantages such as gas adsorption desorption speed, environment friendliness and synthesis step be fast simple and easy.Therefore, no matter in the absorption of carbon dioxide or the storage of hydrogen, metal-organic framework materials all enjoys expectation.
With current metal-organic framework materials, major part uses transition metal (such as: zinc, cobalt, copper, nickel ... Deng) as central metal.For example, the MOF-5 be made up of zinc and Isosorbide-5-Nitrae-benzenedicarboxylic acid, has the carbon dioxide adsorption of about 5wt% under normal temperature and pressure (298K/1bar), but the structure of MOF-5 is very responsive to aqueous vapor, under low-humidity environment, namely crystallinity can be lost.Or with the MOF-177 be made up of zinc and 1,3,5-benzenetribenzoic acid, although MOF-177 adsorbable a large amount of carbon dioxide when high pressure, but material is placed in general environment and will disintegrates after three days.
That is, the metal-organic framework materials centered by transition metal still has suitable improvement space in heat-resisting or water resistant gas etc.In addition, because transition metal is more unfriendly to environment, thus also need extra program to process the transition metal after use.
Summary of the invention
The invention relates to a kind of metal-organic framework materials, Its Preparation Method And Use, use and promote the heat resistance of metal-organic framework materials and the ability of water resistant gas, and solve in prior art the problem needing extra program to process to the unfriendly transition metal of environment.
Metal-organic framework materials disclosed by one embodiment of the invention, has the chemical formula of formula 1.M (OH) (L) (formula 1).Wherein, M is trivalent aluminium ion, and L is 4,4 '-oxydibenzoic acid or 4, two bud dentates of 4 '-stilbenedicarboxylicacid acid.
The preparation method of the metal-organic framework materials disclosed by one embodiment of the invention, comprises following steps.Multiple trivalent aluminium salt is provided.Multiple pairs of bud dentates are provided.The multiple trivalent aluminium salt of blending, multiple pairs of bud dentates and a solvent form a solution, and two bud dentate is 4,4 '-oxydibenzoic acid or 4,4 '-stilbenedicarboxylicacid acid.Heated solution, makes multiple trivalent aluminium salt and multiple pairs of bud dentates form a metal-organic framework materials.
The purposes of the metal-organic framework materials disclosed by one embodiment of the invention, it is for adsorbed gas.
Metal-organic framework materials disclosed by the embodiment of the present invention, Its Preparation Method And Use, owing to being use aluminium and two bud dentate to prepare metal-organic framework materials, and do not need to use transition metal, thus comparatively friendly to environment.On the other hand, because aluminium has stronger bond energy with the co-ordinate covalent bond between two bud dentate, and the metal-organic framework materials formed has special crystallographic system, space group and have special peak value on X-ray difraction spectrum, thus the metal-organic framework materials of the present embodiment has stronger structure, and can exist at the high temperatures of 300 DEG C.Secondly, the metal-organic framework materials disclosed by the embodiment of the present invention has above-mentioned architectural characteristic, thus has the ability of opposing aqueous vapor preferably.Whereby, the present invention, except the ability of the heat resistance and water resistant gas that significantly can promote metal-organic framework materials, also solves in prior art the problem needing extra program to process to the unfriendly transition metal of environment.
The above explanation about content of the present invention and the explanation of following embodiment in order to demonstration and explanation principle of the present invention, and provide claim of the present invention further to explain.
Accompanying drawing explanation
Fig. 1 is the flow chart of the preparation method of the metal-organic framework materials disclosed by one embodiment of the invention.
4 of the metal-organic framework materials of Fig. 2 A disclosed by the embodiment of the present invention one, the coordination environment schematic diagram of 4 '-oxydibenzoic acid.
The coordination environment schematic diagram of the central metal aluminium of the metal-organic framework materials of Fig. 2 B disclosed by the embodiment of the present invention one.
The structural representation of the metal-organic framework materials of Fig. 2 C disclosed by the embodiment of the present invention one.
The X-ray diffracting spectrum of the metal-organic framework materials of Fig. 2 D disclosed by the embodiment of the present invention one.
The test result of the nitrogen adsorption desorption test of the metal-organic framework materials of Fig. 3 disclosed by the embodiment of the present invention one.
The test result of the carbon dioxide adsorption desorption test of the metal-organic framework materials of Fig. 4 A disclosed by the embodiment of the present invention one at the temperature of 293K.
The test result of the carbon dioxide adsorption desorption test of the metal-organic framework materials of Fig. 4 B disclosed by the embodiment of the present invention one at the temperature of 273K.
The test result of the hydrogen adsorption desorption test of the metal-organic framework materials of Fig. 4 C disclosed by the embodiment of the present invention one at the temperature of 77K.
The test result of the thermogravimetric analysis of the metal-organic framework materials of Fig. 5 disclosed by the embodiment of the present invention one.
4 of the metal-organic framework materials of Fig. 6 A disclosed by the embodiment of the present invention two, the coordination environment schematic diagram of 4 '-stilbenedicarboxylicacid acid.
The coordination environment schematic diagram of the central metal aluminium of the metal-organic framework materials of Fig. 6 B disclosed by the embodiment of the present invention two.
The structural representation of the metal-organic framework materials of Fig. 6 C disclosed by the embodiment of the present invention two.
The X-ray diffracting spectrum of the metal-organic framework materials of Fig. 6 D disclosed by the embodiment of the present invention two.
The test result of the nitrogen adsorption desorption test of the metal-organic framework materials of Fig. 7 disclosed by the embodiment of the present invention two.
The test result of the carbon dioxide adsorption desorption test of the metal-organic framework materials of Fig. 8 A disclosed by the embodiment of the present invention two respectively at the temperature of 273K and 293K.
The test result of the hydrogen adsorption desorption test of the metal-organic framework materials of Fig. 8 B disclosed by the embodiment of the present invention two at the temperature of 77K.
The test result of the thermogravimetric analysis of the metal-organic framework materials of Fig. 9 A disclosed by the embodiment of the present invention two.
Alternating temperature-X-ray the diffracting spectrum of the metal-organic framework materials of Fig. 9 B disclosed by the embodiment of the present invention two.
The metal-organic framework materials of Figure 10 A disclosed by the embodiment of the present invention two is soaked in the X-ray diffracting spectrum in water after 7 days.
The metal-organic framework materials of Figure 10 B disclosed by the embodiment of the present invention two is soaked in the test result of the nitrogen adsorption desorption test in water after 7 days at the temperature of 77K.
The metal-organic framework materials of Figure 11 disclosed by the embodiment of the present invention one carries out repeatedly the test result of adsorption desorption test with carbon dioxide.
Detailed description of the invention
Below detailed features of the present invention and advantage is described in embodiments in detail, its content is enough to make those skilled in the art understand technology contents of the present invention and implement according to this, and content, claim and the accompanying drawing disclosed by this description, those skilled in the art can understand the object and advantage that the present invention is correlated with easily.Following embodiment further describes viewpoint of the present invention, but not to limit category of the present invention anyways.
First, refer to Fig. 1, Fig. 1 is the flow chart of the preparation method of the metal-organic framework materials disclosed by one embodiment of the invention.
First, multiple trivalent aluminium salt (S101) is provided.Trivalent aluminium salt is such as but not limited to the aluminum nitrate Al (NO containing nine crystallizations water
3)
39H
2o.In embodiments of the present invention, trivalent aluminium salt also can be the villaumite (AlCl of aluminium
3), sulfate (Al
2(SO
4)
3) or other salts of aluminium, and in aluminium salt the crystallization water number and be not used to limit the present invention.
Then, multiple pairs of bud dentates (S102) are provided.In the present invention, two bud dentate is 4,4 '-oxydibenzoic acid (4,4 '-Oxybisbenzoic acid) or 4,4 '-stilbenedicarboxylicacid acid (4,4 '-stilbenedicarboxylic acid).
Then, blending trivalent aluminium salt, two bud dentate and a solvent form a solution (S103).Wherein, the mole ratio of trivalent aluminium salt and two bud dentate is between 2:1 to 1:3, for example, trivalent aluminium salt and the mole ratio of two bud dentate can be 2: 1,1: 1,1:1.5,1:2 or 1:3.In addition, solvent is such as DMF (N, N-dimethylforamide), N, N-DEF (N, N-diethylforamide), water or its combination.
Finally, heated solution, makes trivalent aluminium salt form a metal-organic framework materials (S104) with two bud dentate.Specifically, be first heat up with the firing rate of 60 DEG C/hr.When temperature is heated to after between 120 DEG C to 200 DEG C, then reaction temperature is maintained within the scope of this, and continue to react.Reaction time, between 24 hours and 72 hours, reacts completely with two bud dentate to make aluminium salt.It is noted that above-mentioned response parameter all can affect the reaction and character thereof of preparing metal-organic framework materials.With firing rate, if the excessive velocities of heating, then trivalent aluminium salt is more incomplete with the reaction of two bud dentate.With reaction temperature, if reaction temperature is too high, then trivalent aluminium salt and two bud dentate may form the metal-organic framework materials of different structure, but if reaction temperature is too low, then trivalent aluminium salt is more incomplete with the reaction of two bud dentate.With the reaction time, if the reaction time is too short, the reaction of trivalent aluminium salt and two bud dentate comparatively not exclusively or can form the metal-organic framework materials of different structure.
Made metal-organic framework materials has the chemical formula of formula 1:
M (OH) (L) (formula 1).
Wherein, M is trivalent aluminium ion, and L is two bud dentates.In embodiments of the present invention, two bud dentate is 4,4 '-oxydibenzoic acid or 4,4 '-stilbenedicarboxylicacid acid.Made metal-organic framework materials has the character of multiple hole, its BET (Brunauer-Emmett-Teller) specific area is between 1004 and 1984 meters squared per gram, and Langmuir specific area is between 1282 and 2575 meters squared per gram.On the other hand, the absorption that the metal-organic framework materials made by the embodiment of the present invention is applied in gas there is good performance.The carbon dioxide adsorption (at absolute temperature 293K) of metal-organic framework materials is between 1.66 to 2.48 mMs/grams, carbon dioxide adsorption (at absolute temperature 273K) is between 2.65 to 4.28 mMs/grams, and hydrogen adsorption amount (at absolute temperature 77K) is between 7.36 to 8.82 mMs/grams.
Below will introduce metal-organic framework materials of the present invention by several embodiment to the present invention and manufacture method elaborates, and carry out experiment test for the ability of the gas absorption character of metal-organic framework materials, heat resistance and water resistant gas.
Embodiment one
First, by the Al (NO of 0.25 mM (mmo1)
3)
39H
2o, 0.25 mM 4,4 '-oxydibenzoic acid (H
2oBA) and the DMF of 6.0 milliliters (mL) (DMF) add a Teflon (Teflon) interior cup.Then, cup in Teflon is placed in an iron cup, and iron cup is put into high temperature furnace.In high temperature furnace, be warming up to 120 DEG C with the firing rate of 60 DEG C/hr.Then, react 2 days under the reaction temperature of 120 DEG C.After question response completes, then with the cooling velocity of 6 DEG C/hr, room temperature is fallen back.Finally, carry out air exhaust filtering, and with second alcohol and water wash products.After to be dried, the white powder of product Compound 1.
The crystallographic system of compound 1 is tetragonal crystal system (tetragonal), and space group is I4
1/ a.Refer to Fig. 2 A to Fig. 2 D, 4 of the metal-organic framework materials of Fig. 2 A disclosed by the embodiment of the present invention one, the coordination environment schematic diagram of 4 '-oxydibenzoic acid.The coordination environment schematic diagram of the central metal aluminium of the metal-organic framework materials of Fig. 2 B disclosed by the embodiment of the present invention one.The structural representation of the metal-organic framework materials of Fig. 2 C disclosed by the embodiment of the present invention one.The X-ray diffracting spectrum of the metal-organic framework materials of Fig. 2 D disclosed by the embodiment of the present invention one.As shown in Figure 2 D, the 2 θ values at first most high-amplitude wave peak of compound 1 are between 6.5 degree and 7.2 degree, and the 2 θ values at second most high-amplitude wave peak are between 8.2 degree and 9.2 degree, and the 2 θ values at the 3rd most high-amplitude wave peak are between 9.5 degree and 10.5 degree.
Then, with ASAP-2020 hole analyzer, nitrogen adsorption desorption test (probe temperature: 77K) is carried out to compound 1.The test result of compound 1 refers to Fig. 3, the test result of the nitrogen adsorption desorption test of the metal-organic framework materials of Fig. 3 disclosed by the embodiment of the present invention one.Then, the result of Fig. 3 is calculated respectively the specific area of compound 1 with the theory of the theory of BET and Langmuir.According to the result of calculation of BET, the BET specific surface area of compound 1 is 1004 meters squared per gram; According to the result of calculation of Langmuir, the Langmuir specific area of compound 1 is 1282 meters squared per gram.Total pore volume of the single-point absorption of compound 1 is 0.56 cubic centimetre/gram.Then, utilize DFT-cylinder-NLDFT theory to calculate the bore hole size of compound 1, the hole size of compound 1 is 10.2 dusts
Then, with the gas sorption ability of ASAP-2020 hole analyzer test compounds 1.Refer to Fig. 4 A to Fig. 4 C, the test result of the carbon dioxide adsorption desorption test of the metal-organic framework materials of Fig. 4 A disclosed by the embodiment of the present invention one at the temperature of 293K, the test result of the carbon dioxide adsorption desorption test of the metal-organic framework materials of Fig. 4 B disclosed by the embodiment of the present invention one at the temperature of 273K, the test result of the hydrogen adsorption desorption test of the metal-organic framework materials of Fig. 4 C disclosed by the embodiment of the present invention one at the temperature of 77K.According to the test result of Fig. 4 A, the adsorbance of the carbon dioxide of compound 1 at the temperature of 293K is 2.48 mMs/gram.According to the test result of Fig. 4 B, the adsorbance of the carbon dioxide of compound 1 at the temperature of 273K is 4.28 mMs/gram.According to the test result of Fig. 4 C, the adsorbance of the hydrogen of compound 1 at the temperature of 77K is 8.82 mMs/gram.
Refer to Fig. 5, the test result of the thermogravimetric analysis of the metal-organic framework materials of Fig. 5 disclosed by the embodiment of the present invention one.Wherein, test carries out under the environment of nitrogen, and be heated to 800 DEG C with the speed of 10 DEG C/min from 30 DEG C, uses the loss in weight of observing compound 1.As shown in Figure 5, when temperature increase is to 200 DEG C, due to the hole inside of compound 1 solvent (such as: DMF or water ... Deng) understand the hole that leave compound 1 because of high-temperature gasification, thus compound 1 about has the loss in weight of 22wt%.Then, when temperature maintains 200 DEG C to 400 DEG C interval, the weight of compound 1 maintains balance, and namely compound 1 can exist at the high temperatures of 400 DEG C.
In the present embodiment, due to aluminium and 4, the co-ordinate covalent bond between 4 ' oxydibenzoic acid has stronger bond energy, and the crystallographic system of the metal-organic framework materials formed is tetragonal crystal system, and its space group is I41/a.And, the 2 θ values at metal-organic framework materials first most high-amplitude wave peak on X-ray difraction spectrum of the present embodiment are between 6.5 degree and 7.2 degree, the 2 θ values at second most high-amplitude wave peak are between 8.2 degree and 9.2 degree, and the 2 θ values at the 3rd most high-amplitude wave peak are between 9.5 degree and 10.5 degree, thus the metal-organic framework materials of the present embodiment has stronger structure.Therefore, the metal-organic framework materials of the present embodiment can exist at the high temperatures of 400 DEG C.
Embodiment two
First, by the Al (NO of 0.5 mM (mmol)
3)
39H
2o, 0.5 mM 4,4 '-stilbenedicarboxylicacid acid (H
2sDA) and the N of 10.0 milliliters (mL), N-DEF (DEF) add cup in a Teflon.Then, cup in Teflon is placed in an iron cup, and iron cup is put into high temperature furnace.In high temperature furnace, be warming up to 180 DEG C with the firing rate of 60 DEG C/hr.Then, react 1 day under the reaction temperature of 180 DEG C.After question response completes, then with the cooling velocity of 6 DEG C/hr, room temperature is fallen back.Finally, carry out air exhaust filtering, and with second alcohol and water wash products.After to be dried, the off-white powder of product Compound 2.
The crystallographic system of compound 2 is rhombic system (orthorhombic), and space group is Imma.Refer to Fig. 6 A to Fig. 6 D, 4 of the metal-organic framework materials of Fig. 6 A disclosed by the embodiment of the present invention two, the coordination environment schematic diagram of 4 '-stilbenedicarboxylicacid acid.The coordination environment schematic diagram of the central metal aluminium of the metal-organic framework materials of Fig. 6 B disclosed by the embodiment of the present invention two.The structural representation of the metal-organic framework materials of Fig. 6 C disclosed by the embodiment of the present invention two.The X-ray diffracting spectrum of the metal-organic framework materials of Fig. 6 D disclosed by the embodiment of the present invention two.As shown in Figure 6 D, 20 values at first of compound 2 most high-amplitude wave peak are between 5.0 degree and 6.0 degree, and the 2 θ values at second most high-amplitude wave peak are between 10.0 degree and 11.0 degree, and the 2 θ values at the 3rd most high-amplitude wave peak are between 13.5 degree and 14.5 degree.
Then, with ASAP-2020 hole analyzer, nitrogen adsorption desorption test (probe temperature: 77K) is carried out to compound 2.The test result of compound 2 refers to Fig. 7, the test result of the nitrogen adsorption desorption test of the metal-organic framework materials of Fig. 7 disclosed by the embodiment of the present invention two.Then, the result of Fig. 7 is calculated respectively the specific area of compound 2 with the theory of the theory of BET and Langmuir.According to the result of calculation of BET, the BET specific surface area of compound 2 is 1984 meters squared per gram; According to the result of calculation of Langmuir, the Langmuir specific area of compound 2 is 2575 meters squared per gram.Total pore volume of the single-point absorption of compound 2 is 1.20 cubic centimetres/gram.Then, utilize DFT-cylinder-NLDFT theory to calculate the bore hole size of compound 2, the hole size of compound 2 is 12,16,18,21 dusts
Then, with the gas sorption ability of ASAP-2020 hole analyzer test compounds 2.Refer to Fig. 8 A and Fig. 8 B, the test result of the carbon dioxide adsorption desorption test of the metal-organic framework materials of Fig. 8 A disclosed by the embodiment of the present invention two respectively at the temperature of 273K and 293K, the test result of the hydrogen adsorption desorption test of the metal-organic framework materials of Fig. 8 B disclosed by the embodiment of the present invention two at the temperature of 77K.According to the test result of Fig. 8 A, the adsorbance of the carbon dioxide of compound 2 at the temperature of 293K is 1.66 mMs/gram, and the adsorbance of the carbon dioxide of compound 2 at the temperature of 273K is 2.65 mMs/gram.According to the test result of Fig. 8 B, the adsorbance of the hydrogen of compound 2 at the temperature of 77K is 7.36 mMs/gram.
Refer to Fig. 9 A, the test result of the thermogravimetric analysis of the metal-organic framework materials of Fig. 9 A disclosed by the embodiment of the present invention two.In figure 9 a, the condition of test is carried out under the environment of nitrogen, and be heated to 800 DEG C with the speed of 10 DEG C/min from 30 DEG C, uses the loss in weight of observing metal-organic framework materials.As shown in Figure 9 A, compound 2 there is no the significantly interim loss in weight.Then, analyzed with alternating temperature-X light diffracting analysis instrument by compound 2, analysis result refers to Fig. 9 B, the alternating temperature-X-ray diffracting spectrum of the metal-organic framework materials of Fig. 9 B disclosed by the embodiment of the present invention two.In figures 9 b and 9, compound 2 is 300 DEG C time, and compound 2 still has obvious characteristic peaks.Namely, compound 2 can exist at the high temperatures of 300 DEG C.That is, in figure 9 a, compound 2 300 DEG C time there is 10%wt the loss in weight be stem from solvent (such as: N, N-DEF or water ... Deng) leave the result of compound 2.
In the present embodiment, due to aluminium and 4, the co-ordinate covalent bond between 4 '-stilbenedicarboxylicacid acid has stronger bond energy, and the crystallographic system of the metal-organic framework materials formed is rhombic system, and its space group is Imma.And, the 2 θ values at metal-organic framework materials first most high-amplitude wave peak on X-ray difraction spectrum of the present embodiment are between 5.0 degree and 6.0 degree, the 2 θ values at second most high-amplitude wave peak are between 10.0 degree and 11.0 degree, and the 2 θ values at the 3rd most high-amplitude wave peak are between 13.5 degree and 14.5 degree, thus the metal-organic framework materials of the present embodiment has stronger structure.Therefore, the metal-organic framework materials of the present embodiment can exist at the high temperatures of 300 DEG C.
Then, the ability of the water resistant gas of the metal-organic framework materials of the embodiment of the present invention is tested.Refer to Figure 10 A and Figure 10 B, the metal-organic framework materials of Figure 10 A disclosed by the embodiment of the present invention two is soaked in the X-ray diffracting spectrum in water after 7 days, and the metal-organic framework materials of Figure 10 B disclosed by the embodiment of the present invention two is soaked in the test result of the nitrogen adsorption desorption test in water after 7 days at the temperature of 77K.As shown in Figure 10 A, compound 2, being soaked in water after 7 days, still has obvious characteristic peaks.That is, compound 2, under the environment of high aqueous vapor, still has complete structure, and thus metal-organic framework materials of the present invention has the ability of opposing aqueous vapor preferably really.
Then, the number of times restriction of the use of the metal-organic framework materials of the embodiment of the present invention is tested.Refer to Figure 11, the metal-organic framework materials of Figure 11 disclosed by the embodiment of the present invention one carries out repeatedly the test result of adsorption desorption test with carbon dioxide.In fig. 11, at carbon dioxide adsorption after metal-organic framework materials, only need to pass into nitrogen and carbon dioxide can be made from metal-organic framework materials desorption, and do not need extra heating schedule to make carbon dioxide from metal-organic framework materials desorption.In addition, when carrying out the test of adsorption desorption repeatedly, the adsorbance of each carbon dioxide is all more than 7wt%.That is, metal-organic framework materials of the present invention has good cyclicity on the adsorption desorption of gas.Namely, when carrying out the desorption of gas, Comparatively speaking without the phenomenon of gas residue at metal-organic framework materials.
Metal-organic framework materials disclosed by the embodiment of the present invention, Its Preparation Method And Use, owing to being use aluminium and two bud dentate to prepare metal-organic framework materials, and do not need to use transition metal, thus comparatively friendly to environment.On the other hand, because aluminium has stronger bond energy with the co-ordinate covalent bond between two bud dentate, and the metal-organic framework materials formed has special crystallographic system, space group and have special peak value on X-ray difraction spectrum, thus the metal-organic framework materials of the present embodiment has stronger structure, and can exist at the high temperatures of 300 DEG C.Secondly, the metal-organic framework materials disclosed by the embodiment of the present invention has above-mentioned architectural characteristic, thus has the ability of opposing aqueous vapor preferably.Whereby, the present invention, except the ability of the heat resistance and water resistant gas that significantly can promote metal-organic framework materials, also solves in prior art the problem needing extra program to process to the unfriendly transition metal of environment.
In addition, the metal-organic framework materials disclosed by the embodiment of the present invention has above-mentioned architectural characteristic, thus on the adsorption desorption of gas, has good cyclicity.
Claims (20)
1. a metal-organic framework materials, is characterized in that, has chemical formula as shown in Equation 1:
M (OH) (L) (formula 1);
Wherein, M is trivalent aluminium ion, and L is 4,4 '-oxydibenzoic acid or 4, two bud dentates of 4 '-stilbenedicarboxylicacid acid.
2. metal-organic framework materials according to claim 1, wherein L is 4,4 '-oxydibenzoic acid, the 2 θ values at first most high-amplitude wave peak of the X-ray diffracting spectrum of this metal-organic framework materials are between 6.5 degree and 7.2 degree, the 2 θ values at second most high-amplitude wave peak of the X-ray diffracting spectrum of this metal-organic framework materials are between 8.2 degree and 9.2 degree, and the 2 θ values at the 3rd most high-amplitude wave peak of the X-ray diffracting spectrum of this metal-organic framework materials are between 9.5 degree and 10.5 degree.
3. metal-organic framework materials according to claim 2, wherein the crystallographic system of this metal-organic framework materials is tetragonal crystal system.
4. metal-organic framework materials according to claim 3, wherein the space group of this metal-organic framework materials is I4
1/ a.
5. metal-organic framework materials according to claim 1, wherein L is 4,4 '-stilbenedicarboxylicacid acid, the 2 θ values at first most high-amplitude wave peak of the X-ray diffracting spectrum of this metal-organic framework materials are between 5.0 degree and 6.0 degree, the 2 θ values at second most high-amplitude wave peak of the X-ray diffracting spectrum of this metal-organic framework materials are between 10.0 degree and 11.0 degree, and the 2 θ values at the 3rd most high-amplitude wave peak of the X-ray diffracting spectrum of this metal-organic framework materials are between 13.5 degree and 14.5 degree.
6. metal-organic framework materials according to claim 5, wherein the crystallographic system of this metal-organic framework materials is rhombic system.
7. metal-organic framework materials according to claim 6, wherein the space group of this metal-organic framework materials is Imma.
8. metal-organic framework materials according to claim 1, wherein the L of the chemical formula as shown in Equation 1 of this metal-organic framework materials is 4, two bud dentates of 4 '-oxydibenzoic acid, the BET specific surface area of this metal-organic framework materials is 1004 meters squared per gram.
9. metal-organic framework materials according to claim 1, wherein the L of the chemical formula as shown in Equation 1 of this metal-organic framework materials is 4, two bud dentates of 4 '-stilbenedicarboxylicacid acid, the BET specific surface area of this metal-organic framework materials is 1984 meters squared per gram.
10. metal-organic framework materials according to claim 1, wherein the L of the chemical formula as shown in Equation 1 of this metal-organic framework materials is 4, two bud dentates of 4 '-oxydibenzoic acid, the Langmuir specific area of this metal-organic framework materials is 1282 meters squared per gram.
11. metal-organic framework materials according to claim 1, wherein the L of the chemical formula as shown in Equation 1 of this metal-organic framework materials is 4, two bud dentates of 4 '-stilbenedicarboxylicacid acid, the Langmuir specific area of this metal-organic framework materials is 2575 meters squared per gram.
12. metal-organic framework materials according to claim 1, wherein the carbon dioxide adsorption of this metal-organic framework materials under absolute temperature 273K is between 2.65 to 4.28 mMs/grams.
13. metal-organic framework materials according to claim 1, wherein the hydrogen adsorption amount of this metal-organic framework materials under absolute temperature 77K is between 7.36 to 8.82 mMs/grams.
The preparation method of 14. 1 kinds of metal-organic framework materials, is characterized in that, comprises:
Multiple trivalent aluminium salt is provided;
There is provided multiple pairs of bud dentates, the plurality of pair of bud dentate is 4,4 '-oxydibenzoic acid or 4,4 '-stilbenedicarboxylicacid acid;
The plurality of trivalent aluminium salt of blending, the plurality of pair of bud dentate and a solvent form a solution; And
Heat this solution, make the plurality of trivalent aluminium salt and the plurality of pair of bud dentate form a metal-organic framework materials.
The preparation method of 15. metal-organic framework materials according to claim 14, wherein at the plurality of trivalent aluminium salt of this blending, the plurality of pair of bud dentate and a solvent in the step of a solution, this solvent is DMF, N, N-DEF, water or its combination.
The preparation method of 16. metal-organic framework materials according to claim 14, wherein formed in the step of a solution at the plurality of trivalent aluminium salt of this blending, the plurality of pair of bud dentate and a solvent, the mole ratio of the plurality of trivalent aluminium salt and the plurality of pair of bud dentate is between 2:1 to 1:3.
The preparation method of 17. metal-organic framework materials according to claim 14, wherein in the step of this this solution of heating, reaction temperature is between 120 DEG C to 200 DEG C.
The preparation method of 18. metal-organic framework materials according to claim 14, wherein in the step of this this solution of heating, reaction temperature heats up with the firing rate of 60 DEG C/hr.
The preparation method of 19. metal-organic framework materials according to claim 14, wherein in the step of this this solution of heating, the reaction time is little between 72 hours between 24.
The purposes of 20. 1 kinds of metal-organic framework materials according to claim 1, is characterized in that, it is for adsorbed gas.
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