CN104338513B - 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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- CN104338513B CN104338513B CN201310428964.1A CN201310428964A CN104338513B CN 104338513 B CN104338513 B CN 104338513B CN 201310428964 A CN201310428964 A CN 201310428964A CN 104338513 B CN104338513 B CN 104338513B
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- 239000000463 material Substances 0.000 title claims abstract description 141
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 133
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- 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 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 42
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 20
- 239000001569 carbon dioxide Substances 0.000 claims description 20
- 159000000013 aluminium salts Chemical class 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000001228 spectrum Methods 0.000 claims description 17
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 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
- 230000004044 response Effects 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
- 239000000203 mixture Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 7
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract description 3
- 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
- 229940125782 compound 2 Drugs 0.000 description 24
- 238000002336 sorption--desorption measurement Methods 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 229960004424 carbon dioxide Drugs 0.000 description 21
- 229940125904 compound 1 Drugs 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 229910052723 transition metal Inorganic materials 0.000 description 9
- 150000003624 transition metals Chemical class 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000004809 Teflon Substances 0.000 description 5
- 229920006362 Teflon® Polymers 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- 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 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- 241000790917 Dioxys <bee> Species 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 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 description 3
- 239000013384 organic framework Substances 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
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 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 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241001580033 Imma Species 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000013236 Zn4O(BTB)2 Substances 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000003860 storage 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
- 101000905241 Mus musculus Heart- and neural crest derivatives-expressed protein 1 Proteins 0.000 description 1
- -1 N-diethylforamide) Inorganic materials 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
- ZEEBGORNQSEQBE-UHFFFAOYSA-N [2-(3-phenylphenoxy)-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound C1(=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)C1=CC=CC=C1 ZEEBGORNQSEQBE-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 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
- 238000003795 desorption Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 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
- 238000005304 joining Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000926 separation method Methods 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
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing 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
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 present invention is with regard to a kind of metal-organic framework materials, Its Preparation Method And Use, and particularly one kind has three
The metal-organic framework materials of valency aluminium ion and double bud dentate, Its Preparation Method And Use.
Background technology
Metal-organic framework materials (Metal-Organic Frameworks, MOFs) are having of developing rapidly in recent years
Machine-inorganic coordination polymers.In general, metal-organic framework materials be bonded by central metal and organic coordination base and
Become.And, the stack manner according to the central metal in metal-organic framework materials and organic coordination base, metallic organic framework material
Material also can further discriminate between out one-dimensional, two-dimentional and three-dimensional arrangement species.
Metal-organic framework materials are a kind of porous materials.In general, porous material is due to having more hole
Hole, larger specific surface area, thus often it is used in the fields such as gas absorption, gas separation, catalysis, sensing element, particularly
Field in the absorption with hydrogen for the carbon dioxide and storage.For example, porous material can be arranged on titanium dioxide by user
At the discharge of carbon, use absorbing carbon dioxide, to reduce the impact to environment for the carbon dioxide.On the other hand, porous material
Can use and replace the mode to store liquefaction hydrogen through steel cylinder as Recent Progress in Hydrogen Storage Materials.
Compared to the porous material of other species, metal-organic framework materials have the advantages that structure change is various.Cause
This, user can adjust composition and the hole size of metal-organic framework materials according to its demand.Additionally, in application
On, metal-organic framework materials have higher gas absorption amount in low pressure, and metal-organic framework materials also have
Quickly gas adsorption desorption speed, the friendly property of environment and synthesis step simple the advantages of.Therefore, no matter in the suction of carbon dioxide
The storage of attached or hydrogen, metal-organic framework materials all enjoy expectation.
For current metal-organic framework materials, major part is using transition metal (for example：Zinc, cobalt, copper, nickel ...
Deng) as central metal.For example, the MOF-5 being made up of with Isosorbide-5-Nitrae-benzenedicarboxylic acid zinc, normal
There is under normal temperature and pressure (298K/1bar) carbon dioxide adsorption of about 5wt%, but the structure of MOF-5 be extremely sensitive to aqueous vapor,
Crystallinity can be lost under low-humidity environment.Or, so that by zinc and 1,3,5-benzenetribenzoic acid are formed
MOF-177 for although MOF-177 adsorbable substantial amounts of carbon dioxide in high pressure, but material is placed on general environment
In will disintegrate after three days.
That is, metal-organic framework materials centered on transition metal still have phase at aspects such as heat-resisting or water resistant gas
When improvement space.Further, since transition metal is more unfriendly to environment, thus it is also required to extra program to process after use
Transition metal.
Content of the invention
The present invention is with regard to a kind of metal-organic framework materials, Its Preparation Method And Use, uses lifting metal organic
The thermostability of framework material and the ability of water resistant gas, and solve in prior art, to need extra program to process to environment not
The problem of friendly transition metal.
Metal-organic framework materials disclosed by one embodiment of the invention, have the chemical formula of formula 1.M (OH) (L) is (public
Formula 1).Wherein, M is trivalent aluminium ion, and L is 4,4 '-oxydibenzoic acid or 4, double bud coordinations of 4 '-stilbenedicarboxylicacid acid
Base.
The preparation method of the metal-organic framework materials disclosed by one embodiment of the invention, comprises the steps of.There is provided many
Individual trivalent aluminium salt.Multiple pairs of bud dentates are provided.Blend multiple trivalent aluminium salt, that the multiple pairs of bud dentates and a solvent form one is molten
Liquid, double bud dentates are 4,4 '-oxydibenzoic acid or 4,4 '-stilbenedicarboxylicacid acid.Heated solution, makes multiple trivalent aluminium salt
Form metal-organic framework materials with multiple pairs of bud dentates.
The purposes of the metal-organic framework materials disclosed by one embodiment of the invention, it is for adsorbed gas.
Disclosed metal-organic framework materials, Its Preparation Method And Use according to embodiments of the present invention, due to being to make
Prepare metal-organic framework materials with aluminum with double bud dentates, without using transition metal, thus more friendly to environment.
On the other hand, because aluminum has stronger bond energy with the co-ordinate covalent bond between double bud dentates, and the metal being formed has
Machine framework material has special crystallographic system, space group and has special peak value on X-ray diffraction spectrum, thus the present embodiment
Metal-organic framework materials there is stronger structure, and can exist in 300 DEG C of high temperatures.Secondly as the present invention
Metal-organic framework materials disclosed by embodiment have above-mentioned architectural characteristic, thus have the preferable energy resisting aqueous vapor
Power.Whereby, the present invention, except the thermostability of metal-organic framework materials and the ability of water resistant gas can be substantially improved, also solves existing
Have and in technology, need extra program to process the problem to the unfriendly transition metal of environment.
The explanation of the above explanation with regard to present invention and following embodiment is in order to demonstrate and to explain the present invention
Principle, and provide the claim of the present invention further to explain.
Brief description
Fig. 1 is the flow chart of the preparation method of the metal-organic framework materials according to disclosed by one embodiment of the invention.
Fig. 2A is 4 of the metal-organic framework materials disclosed by the embodiment of the present invention one, the coordination of 4 '-oxydibenzoic acid
Environment schematic.
Fig. 2 B is that the coordination environment of the central metal aluminum of metal-organic framework materials disclosed by the embodiment of the present invention one shows
It is intended to.
Fig. 2 C is the structural representation of the metal-organic framework materials disclosed by the embodiment of the present invention one.
Fig. 2 D is the X-ray diffracting spectrum of the metal-organic framework materials disclosed by the embodiment of the present invention one.
Fig. 3 is the test knot of the nitrogen adsorption desorption test of the metal-organic framework materials disclosed by the embodiment of the present invention one
Really.
Carbon dioxide at a temperature of 293K for the metal-organic framework materials disclosed by the embodiment of the present invention one for Fig. 4 A
The test result of adsorption desorption test.
Carbon dioxide at a temperature of 273K for the metal-organic framework materials disclosed by the embodiment of the present invention one for Fig. 4 B
The test result of adsorption desorption test.
Hydrogen adsorption desorption at a temperature of 77K for the metal-organic framework materials disclosed by the embodiment of the present invention one for Fig. 4 C
The test result of test.
Fig. 5 is the test result of the thermogravimetric analysiss of metal-organic framework materials disclosed by the embodiment of the present invention one.
Fig. 6 A is 4 of the metal-organic framework materials disclosed by the embodiment of the present invention two, the joining of 4 '-stilbenedicarboxylicacid acid
Position environment schematic.
Fig. 6 B is that the coordination environment of the central metal aluminum of metal-organic framework materials disclosed by the embodiment of the present invention two shows
It is intended to.
Fig. 6 C is the structural representation of the metal-organic framework materials disclosed by the embodiment of the present invention two.
Fig. 6 D is the X-ray diffracting spectrum of the metal-organic framework materials disclosed by the embodiment of the present invention two.
Fig. 7 is the test knot of the nitrogen adsorption desorption test of the metal-organic framework materials disclosed by the embodiment of the present invention two
Really.
Metal-organic framework materials disclosed by the embodiment of the present invention two for Fig. 8 A are respectively in the temperature of 273K and 293K
Under carbon dioxide adsorption desorption test test result.
Hydrogen adsorption desorption at a temperature of 77K for the metal-organic framework materials disclosed by the embodiment of the present invention two for Fig. 8 B
The test result of test.
Fig. 9 A is the test result of the thermogravimetric analysiss of metal-organic framework materials disclosed by the embodiment of the present invention two.
Fig. 9 B is the alternating temperature-X-ray diffracting spectrum of the metal-organic framework materials disclosed by the embodiment of the present invention two.
Figure 10 A be the embodiment of the present invention two disclosed by metal-organic framework materials be soaked in 7 days in water after X-ray diffraction
Collection of illustrative plates.
Figure 10 B be the embodiment of the present invention two disclosed by metal-organic framework materials be soaked in 7 days in water after 77K temperature
The test result of the nitrogen adsorption desorption test under degree.
Figure 11 is that the metal-organic framework materials disclosed by the embodiment of the present invention one carry out multiple adsorption desorption with carbon dioxide
The test result of test.
Specific embodiment
Hereinafter detailed features and the advantage of the present invention are described in embodiments in detail, its content be enough to make this area skill
Art personnel understand that the technology contents of the present invention are simultaneously implemented according to this, and the content according to disclosed by this specification, claim and attached
Figure, skilled person readily understands that the related purpose of the present invention and advantage.Below example is detailed further
The viewpoint of the present invention is described, but not anyways to limit scope of the invention.
First, refer to Fig. 1, Fig. 1 is the preparation of the metal-organic framework materials according to disclosed by one embodiment of the invention
The flow chart of method.
First, multiple trivalent aluminium salt (S101) are provided.Trivalent aluminium salt such as but not limited to contains the aluminum nitrate of nine water of crystallization
Al(NO3)3·9H2O.In embodiments of the present invention, trivalent aluminium salt can also be the villaumite (AlCl of aluminum3), sulfate (Al2
(SO4)3) or other salts, and aluminium salt of aluminum in the number of water of crystallization be not limited to the present invention.
Then, multiple pairs of bud dentates (S102) are provided.In the present invention, double bud dentates are 4,4 '-diphenyl ether diformazan
Sour (4,4 '-Oxybisbenzoic acid) or 4,4 '-stilbenedicarboxylicacid acid (4,4 '-stilbenedicarboxylic
acid).
Then, blend trivalent aluminium salt, double bud dentate and a solvent and form a solution (S103).Wherein, trivalent aluminium salt with
The mole ratio of double bud dentates is between 2：1 to 1：Between 3, for example, the molal quantity of trivalent aluminium salt and double bud dentates
Ratio can be 2: 1,1: 1,1：1.5、1：2 or 1：3.Additionally, solvent is, for example, DMF (N, N-
Dimethylforamide), N, N- diethylformamide (N, N-diethylforamide), water or a combination thereof.
Finally, heated solution, makes trivalent aluminium salt form metal-organic framework materials (S104) with double bud dentates.In detail
For, it is first to be heated up with the firing rate of 60 DEG C/hr.After temperature is heated between 120 DEG C to 200 DEG C, then
Reaction temperature is maintained within this range, and is persistently reacted.Response time is between 24 hours and 72 hours, so that aluminum
Salt reacts complete with double bud dentates.It is noted that above-mentioned response parameter all can affect to prepare metal-organic framework materials
Reaction and its property.For firing rate, if the excessive velocities of heating, then the reaction of trivalent aluminium salt and double bud dentates is relatively
Not exclusively.For reaction temperature, if reaction temperature is too high, trivalent aluminium salt may form different knots from double bud dentates
The metal-organic framework materials of structure, if however, reaction temperature is too low, trivalent aluminium salt is less complete with the reaction of double bud dentates
Entirely.For the response time, if the response time is too short, trivalent aluminium salt relatively incompletely or can be formed with the reaction of double bud dentates
The metal-organic framework materials of different structure.
Made metal-organic framework materials have the chemical formula of formula 1：
M (OH) (L) (formula 1).
Wherein, M is trivalent aluminium ion, and L is double bud dentate.In embodiments of the present invention, double bud dentates be 4,4 '-
Oxydibenzoic acid or 4,4 '-stilbenedicarboxylicacid acid.Made metal-organic framework materials have the property of multiple hole
Matter, its BET (Brunauer Emmett Teller) specific surface area between 1004 and 1984 meters squared per gram, and
Langmuir specific surface area is between 1282 and 2575 meters squared per gram.On the other hand, the metal made by the embodiment of the present invention
Organic framework material is applied good performance in the absorption of gas.The carbon dioxide adsorption of metal-organic framework materials
(in absolute temperature 293K), between 1.66 to 2.48 mMs/grams, carbon dioxide adsorption (in absolute temperature 273K) is situated between
Between 2.65 to 4.28 mMs/grams, and hydrogen adsorption amount (in absolute temperature 77K) is between 7.36 to 8.82 mMs/grams
Between.
By several embodiments, the present invention will be introduced with metal-organic framework materials and its manufacture method of the present invention below
Elaborate, and carry out reality for the ability of the gas absorption property, thermostability and water resistant gas of metal-organic framework materials
Test tries.
Embodiment one
First, by the Al (NO of 0.25 mM (mmo1)3)3·9H2O, the 4 of 0.25 mM, 4 '-oxydibenzoic acid
(H2) and the N,N-dimethylformamide (DMF) of 6.0 milliliters (mL) adds a Teflon (Teflon) interior cup OBA.Then, will
In Teflon, cup is placed in a ferrum cup, and ferrum cup is put in high temperature furnace.In high temperature furnace, with the firing rate liter of 60 DEG C/hr
Temperature is to 120 DEG C.Then, react 2 days under 120 DEG C of reaction temperature.After the completion of question response, then the rate of cooling fall with 6 DEG C/hr
Return room temperature.Finally, carry out pumping to filter, and with second alcohol and water wash products.After to be dried, you can obtain the white of product Compound 1
Color powder.
The crystallographic system of compound 1 is tetragonal crystal system (tetragonal), and space group is I41/a.Refer to Fig. 2A to figure
2D, Fig. 2A are 4 of the metal-organic framework materials disclosed by the embodiment of the present invention one, the coordination environment of 4 '-oxydibenzoic acid
Schematic diagram.Fig. 2 B is that the coordination environment of the central metal aluminum of metal-organic framework materials disclosed by the embodiment of the present invention one is illustrated
Figure.Fig. 2 C is the structural representation of the metal-organic framework materials disclosed by the embodiment of the present invention one.Fig. 2 D is implemented for the present invention
The X-ray diffracting spectrum of the metal-organic framework materials disclosed by example one.As shown in Figure 2 D, first strong wave peak of compound 1
2 θ values between 6.5 degree and 7.2 degree, 2 θ values of second strong wave peak between 8.2 degree and 9.2 degree, and the 3rd
2 θ values of strong wave peak are between 9.5 degree and 10.5 degree.
Then, nitrogen adsorption desorption test (test temperature is carried out with ASAP-2020 hole analyzer to compound 1：77K).
The test result of compound 1 refers to Fig. 3, and Fig. 3 is the nitrogen of the metal-organic framework materials disclosed by the embodiment of the present invention one
The test result of adsorption desorption test.Then, the result of Fig. 3 to be calculated with the theory of the theory of BET and Langmuir respectively
The specific surface area of compound 1.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 surface area of compound 1 is 1282 meters squared per gram.The single-point absorption of compound 1
Total pore volume be 0.56 cubic centimetre/gram.Then, calculate compound 1 using DFT-cylinder-NLDFT theory
Bore hole size, the hole size of compound 1 is 10.2 angstroms
Then, with the gas sorption ability of ASAP-2020 hole analyzer test compound 1.Refer to Fig. 4 A to Fig. 4 C,
Carbon dioxide adsorption desorption at a temperature of 293K for the metal-organic framework materials disclosed by the embodiment of the present invention one for Fig. 4 A is surveyed
The test result of examination, dioxy at a temperature of 273K for the metal-organic framework materials disclosed by the embodiment of the present invention one for Fig. 4 B
Change the test result of carbon adsorption desorption test, metal-organic framework materials disclosed by the embodiment of the present invention one for Fig. 4 C are 77K's
At a temperature of hydrogen adsorption desorption test test result.According to the test result of Fig. 4 A, compound 1 at a temperature of 293K two
The adsorbance of carbonoxide is 2.48 mMs/gram.According to the test result of Fig. 4 B, dioxy at a temperature of 273K for the compound 1
The adsorbance changing carbon is 4.28 mMs/gram.According to the test result of Fig. 4 C, the suction of hydrogen at a temperature of 77K for the compound 1
Attached amount is 8.82 mMs/gram.
Refer to Fig. 5, Fig. 5 is the test of the thermogravimetric analysiss of metal-organic framework materials disclosed by the embodiment of the present invention one
Result.Wherein, test is to carry out in the environment of nitrogen, and is to be heated to 800 DEG C with the speed of 10 DEG C/min from 30 DEG C, mat
To observe the weight loss of compound 1.As shown in figure 5, when temperature rises to 200 DEG C, due within the hole of compound 1
Solvent is (for example：DMF or water ... etc.) understand the hole that leave compound 1 because of high-temperature gasification, thus chemical combination
Thing 1 there are about the weight loss of 22wt%.Then, when temperature maintains 200 DEG C to 400 DEG C interval, the weight dimension of compound 1
Maintain an equal level weighing apparatus, that is, compound 1 can exist in 400 DEG C of high temperatures.
In the present embodiment, due to aluminum 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 being formed is tetragonal crystal system, and its space group is I41/a.And, the present embodiment
Metal-organic framework materials first strong wave peak on X-ray diffraction spectrum 2 θ values between 6.5 degree and 7.2 degree,
2 θ values of two strong wave peaks are between 8.2 degree and 9.2 degree, and 2 θ values of the 3rd strong wave peak are between 9.5 degree and 10.5
Between degree, thus the metal-organic framework materials of the present embodiment have stronger structure.Therefore, the organic bone of the metal of the present embodiment
Frame material can exist in 400 DEG C of high temperatures.
Embodiment two
First, by the Al (NO of 0.5 mM (mmol)3)3·9H2O, the 4 of 0.5 mM, 4 '-stilbenedicarboxylicacid acid
(H2SDA) and 10.0 milliliters (mL) N, N- diethylformamide (DEF) add a Teflon in cup.Then, by Teflon
Interior cup is placed in a ferrum cup, and ferrum cup is put in high temperature furnace.In high temperature furnace, it is warming up to 180 with the firing rate of 60 DEG C/hr
℃.Then, react 1 day under 180 DEG C of reaction temperature.After the completion of question response, then room temperature is dropped back to the rate of cooling of 6 DEG C/hr.
Finally, carry out pumping to filter, and with second alcohol and water wash products.After to be dried, you can obtain the milky white toner of product Compound 2
End.
The crystallographic system of compound 2 is rhombic system (orthorhombic), and space group is Imma.Refer to Fig. 6 A to figure
6D, Fig. 6 A is 4 of the metal-organic framework materials disclosed by the embodiment of the present invention two, the coordination ring of 4 '-stilbenedicarboxylicacid acid
Border schematic diagram.Fig. 6 B is that the coordination environment of the central metal aluminum of metal-organic framework materials disclosed by the embodiment of the present invention two shows
It is intended to.Fig. 6 C is the structural representation of the metal-organic framework materials disclosed by the embodiment of the present invention two.Fig. 6 D is that the present invention is real
Apply the X-ray diffracting spectrum of the metal-organic framework materials disclosed by example two.As shown in Figure 6 D, first high-amplitude wave of compound 2
20 values at peak between 5.0 degree and 6.0 degree, 2 θ values of second strong wave peak between 10.0 degree and 11.0 degree, and the
2 θ values of three strong wave peaks are between 13.5 degree and 14.5 degree.
Then, nitrogen adsorption desorption test (test temperature is carried out with ASAP-2020 hole analyzer to compound 2：77K).
The test result of compound 2 refers to Fig. 7, and Fig. 7 is the nitrogen of the metal-organic framework materials disclosed by the embodiment of the present invention two
The test result of adsorption desorption test.Then, the result of Fig. 7 to be calculated with the theory of the theory of BET and Langmuir respectively
The specific surface area of compound 2.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 surface area of compound 2 is 2575 meters squared per gram.The single-point absorption of compound 2
Total pore volume be 1.20 cubic centimetres/gram.Then, calculate compound 2 using DFT-cylinder-NLDFT theory
Bore hole size, the hole size of compound 2 is 12,16,18,21 angstroms
Then, with the gas sorption ability of ASAP-2020 hole analyzer test compound 2.Refer to Fig. 8 A and Fig. 8 B,
Fig. 8 A is the metal-organic framework materials dioxy at a temperature of 273K and 293K respectively disclosed by the embodiment of the present invention two
Change the test result of carbon adsorption desorption test, metal-organic framework materials disclosed by the embodiment of the present invention two for Fig. 8 B are 77K's
At a temperature of hydrogen adsorption desorption test test result.According to the test result of Fig. 8 A, compound 2 at a temperature of 293K two
The adsorbance of carbonoxide is 1.66 mMs/gram, and the adsorbance of carbon dioxide at a temperature of 273K for the compound 2 is 2.65
MM/gram.According to the test result of Fig. 8 B, the adsorbance of hydrogen at a temperature of 77K for the compound 2 is 7.36 mMs/
Gram.
Refer to Fig. 9 A, Fig. 9 A is the survey of the thermogravimetric analysiss of metal-organic framework materials disclosed by the embodiment of the present invention two
Test result.In figure 9 a, the condition of test is to carry out in the environment of nitrogen, and is to be added from 30 DEG C with the speed of 10 DEG C/min
Heat, to 800 DEG C, uses the weight loss observing metal-organic framework materials.As shown in Figure 9 A, compound 2 has no the obvious stage
The weight loss of property.Then, compound 2 is analyzed with alternating temperature-X light diffracting analysis instrument, analysis result refers to Fig. 9 B, figure
9B is the alternating temperature-X-ray diffracting spectrum of the metal-organic framework materials disclosed by the embodiment of the present invention two.In figures 9 b and 9, compound 2
When 300 DEG C, compound 2 still has obvious characteristic peaks.It is, compound 2 can be deposited in 300 DEG C of high temperatures
?.That is, in figure 9 a, compound 2 weight loss of had 10%wt when 300 DEG C is derived from solvent (for example：
N, N- diethylformamide or water ... etc.) leave the result of compound 2.
In the present embodiment, due to aluminum and 4, the co-ordinate covalent bond between 4 '-stilbenedicarboxylicacid acid has stronger key
Can, and the crystallographic system of the metal-organic framework materials being formed is rhombic system, and its space group is Imma.And, this enforcement
2 θ values of metal-organic framework materials first strong wave peak on X-ray diffraction spectrum of example between 5.0 degree and 6.0 degree,
2 θ values of second strong wave peak between 10.0 degree and 11.0 degree, and 2 θ values of the 3rd strong wave peak between 13.5 degree with
Between 14.5 degree, thus the metal-organic framework materials of the present embodiment have stronger structure.Therefore, the metal of the present embodiment has
Machine framework material can exist in 300 DEG C of high temperatures.
Then, the ability of the water resistant gas of metal-organic framework materials of the test embodiment of the present invention.Refer to Figure 10 A and figure
10B, Figure 10 A be the embodiment of the present invention two disclosed by metal-organic framework materials be soaked in 7 days in water after X-ray diffraction pattern
Spectrum, Figure 10 B be the embodiment of the present invention two disclosed by metal-organic framework materials be soaked in 7 days in water after at a temperature of 77K
Nitrogen adsorption desorption test test result.As shown in Figure 10 A, compound 2, after 7 days in being soaked in water, still has significantly
Characteristic peaks.That is, compound 2 is in the environment of high aqueous vapor, still there is complete structure, thus the metal of the present invention
Organic framework material has the preferable ability resisting aqueous vapor really.
Then, the number of times of the use of metal-organic framework materials of the test embodiment of the present invention limits.Refer to Figure 11, figure
11 metal-organic framework materials disclosed by the embodiment of the present invention one carry out the test of multiple adsorption desorption test with carbon dioxide
Result.In fig. 11, in carbon dioxide adsorption after metal-organic framework materials it is only necessary to be passed through nitrogen can make carbon dioxide
From metal-organic framework materials desorption, carbon dioxide is made to take off from metal-organic framework materials without extra heating schedule
Attached.Additionally, when carrying out multiple adsorption desorption test, the adsorbance of each carbon dioxide is all more than 7wt%.That is, this
The metal-organic framework materials of invention have preferable cyclicity on the adsorption desorption of gas.It is, carrying out the de- of gas
When attached, Comparatively speaking no gas remains in the phenomenon of metal-organic framework materials.
Disclosed metal-organic framework materials, Its Preparation Method And Use according to embodiments of the present invention, due to being to make
Prepare metal-organic framework materials with aluminum with double bud dentates, without using transition metal, thus more friendly to environment.
On the other hand, because aluminum has stronger bond energy with the co-ordinate covalent bond between double bud dentates, and the metal being formed has
Machine framework material has special crystallographic system, space group and has special peak value on X-ray diffraction spectrum, thus the present embodiment
Metal-organic framework materials there is stronger structure, and can exist in 300 DEG C of high temperatures.Secondly as the present invention
Metal-organic framework materials disclosed by embodiment have above-mentioned architectural characteristic, thus have the preferable energy resisting aqueous vapor
Power.Whereby, the present invention, except the thermostability of metal-organic framework materials and the ability of water resistant gas can be substantially improved, also solves existing
Have and in technology, need extra program to process the problem to the unfriendly transition metal of environment.
Further, since the metal-organic framework materials disclosed by the embodiment of the present invention have above-mentioned architectural characteristic, thus
Preferable cyclicity is had on the adsorption desorption of gas.
Claims (13)
1. a kind of metal-organic framework materials are it is characterised in that have chemical formula as shown in Equation 1：
M (OH) (L) (formula 1)；
Wherein, M is trivalent aluminium ion,
Wherein L is 4,4 '-oxydibenzoic acid, first strong wave peak of the X-ray diffracting spectrum of this metal-organic framework materials
2 θ values between 6.5 degree and 7.2 degree, the 2 of second strong wave peak of the X-ray diffracting spectrum of this metal-organic framework materials
θ value between 8.2 degree and 9.2 degree, 2 θ values of the 3rd strong wave peak of the X-ray diffracting spectrum of this metal-organic framework materials
Between between 9.5 degree and 10.5 degree.
2. metal-organic framework materials according to claim 1, the wherein crystallographic system of this metal-organic framework materials are four directions
Crystallographic system.
3. metal-organic framework materials according to claim 2, the wherein space group of this metal-organic framework materials are I41/
a.
4. metal-organic framework materials according to claim 1, wherein this metal-organic framework materials are as shown in Equation 1
The L of chemical formula be 4, double bud dentates of 4 '-oxydibenzoic acid, the BET specific surface area of this metal-organic framework materials is
1004 meters squared per gram.
5. metal-organic framework materials according to claim 1, wherein this metal-organic framework materials are as shown in Equation 1
Chemical formula L be 4, double bud dentates of 4 '-oxydibenzoic acid, the Langmuir specific surface of this metal-organic framework materials
Amass as 1282 meters squared per gram.
6. metal-organic framework materials according to claim 1, wherein this metal-organic framework materials is in absolute temperature
Carbon dioxide adsorption under 273K is between 2.65 to 4.28 mMs/grams.
7. metal-organic framework materials according to claim 1, wherein this metal-organic framework materials is in absolute temperature 77K
Under hydrogen adsorption amount between 7.36 to 8.82 mMs/grams.
8. a kind of preparation method of metal-organic framework materials is it is characterised in that comprise：
Multiple trivalent aluminium salt are provided；
There is provided multiple pairs of bud dentates, the plurality of pair of bud dentate is 4,4 '-oxydibenzoic acid；
Blend the plurality of trivalent aluminium salt, the plurality of pair of bud dentate forms a solution with a solvent；And
Heat this solution, make the plurality of trivalent aluminium salt form metal-organic framework materials with the plurality of pair of bud dentate；
2 θ values of first strong wave peak of the X-ray diffracting spectrum of this metal-organic framework materials between 6.5 degree with 7.2 degree it
Between, 2 θ values of second strong wave peak of the X-ray diffracting spectrum of this metal-organic framework materials between 8.2 degree and 9.2 degree,
2 θ values of the 3rd strong wave peak of the X-ray diffracting spectrum of this metal-organic framework materials are between 9.5 degree and 10.5 degree.
9. the preparation method of metal-organic framework materials according to claim 8, wherein in the plurality of trivalent aluminium of this blending
, in the step of a solution, this solvent is DMF, N, N- diethyl for salt, the plurality of pair of bud dentate and a solvent
Base Methanamide, water or a combination thereof.
10. the preparation method of metal-organic framework materials according to claim 8, wherein in the plurality of trivalent aluminium of this blending
Salt, the plurality of pair of bud dentate form in the step of a solution with a solvent, and the plurality of trivalent aluminium salt is coordinated with the plurality of pair of bud
The mole ratio of base is between 2:1 to 1:Between 3.
The preparation method of 11. metal-organic framework materials according to claim 8, wherein in the step of this this solution of heating
In, reaction temperature is between 120 DEG C to 200 DEG C.
The preparation method of 12. metal-organic framework materials according to claim 8, wherein in the step of this this solution of heating
In, reaction temperature is to be heated up with the firing rate of 60 DEG C/hr.
The preparation method of 13. metal-organic framework materials according to claim 8, wherein in the step of this this solution of heating
In, the response time is between 24 hours to 72 hours.
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| WO2013019865A2 (en) * | 2011-08-01 | 2013-02-07 | Massachusetts Institute Of Technology | Porous catalytic matrices for elimination of toxicants found in tobacco combustion products |
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| WO2013019865A2 (en) * | 2011-08-01 | 2013-02-07 | Massachusetts Institute Of Technology | Porous catalytic matrices for elimination of toxicants found in tobacco combustion products |
| CN102962037A (en) * | 2012-11-01 | 2013-03-13 | 中国科学院大连化学物理研究所 | Metal-organic framework material for methane adsorption separation and preparation method thereof |
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