CN110982083B - A kind of microporous metal organic framework material used as a getter for vacuum heat insulation panel and its synthesis method - Google Patents
A kind of microporous metal organic framework material used as a getter for vacuum heat insulation panel and its synthesis method Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 30
- 238000009413 insulation Methods 0.000 title claims abstract description 29
- 239000013336 microporous metal-organic framework Substances 0.000 title claims abstract description 20
- 238000001308 synthesis method Methods 0.000 title claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- YCPHARWZXFOTPT-UHFFFAOYSA-N 2,6-diethoxyterephthalic acid Chemical compound CCOC1=CC(C(O)=O)=CC(OCC)=C1C(O)=O YCPHARWZXFOTPT-UHFFFAOYSA-N 0.000 claims abstract description 8
- KVQMUHHSWICEIH-UHFFFAOYSA-N 6-(5-carboxypyridin-2-yl)pyridine-3-carboxylic acid Chemical compound N1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=N1 KVQMUHHSWICEIH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- JGILZSHHECIWTA-UHFFFAOYSA-N 2,5-diethylterephthalic acid Chemical compound CCC1=CC(C(O)=O)=C(CC)C=C1C(O)=O JGILZSHHECIWTA-UHFFFAOYSA-N 0.000 claims abstract description 4
- FKUJGZJNDUGCFU-UHFFFAOYSA-N 2,5-dimethylterephthalic acid Chemical compound CC1=CC(C(O)=O)=C(C)C=C1C(O)=O FKUJGZJNDUGCFU-UHFFFAOYSA-N 0.000 claims abstract description 4
- SIQYOFNSIZEILQ-UHFFFAOYSA-N 2,6-dimethylterephthalic acid Chemical compound CC1=CC(C(O)=O)=CC(C)=C1C(O)=O SIQYOFNSIZEILQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- GUIDAAAVTIRHLQ-UHFFFAOYSA-N 4-[4-(4-carboxyphenyl)-2,5-dimethoxyphenyl]benzoic acid Chemical compound COc1cc(c(OC)cc1-c1ccc(cc1)C(O)=O)-c1ccc(cc1)C(O)=O GUIDAAAVTIRHLQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- LSVBHPJRODVLNG-UHFFFAOYSA-N 4-[4-(4-carboxyphenyl)-2,5-dipropylphenyl]benzoic acid Chemical compound C(CC)C1=C(C=C(C(=C1)C1=CC=C(C=C1)C(=O)O)CCC)C1=CC=C(C=C1)C(=O)O LSVBHPJRODVLNG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- JZDSTRMMQZSYFF-UHFFFAOYSA-N 4-[4-(4-carboxyphenyl)-2,5-dimethylphenyl]benzoic acid Chemical compound C1(C(=CC(C(=C1)C)=C1C=CC(C(=O)O)=C[CH]1)C)=C1C=CC(C(=O)O)=C[CH]1 JZDSTRMMQZSYFF-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000013110 organic ligand Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 claims description 5
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 5
- XRXMNWGCKISMOH-UHFFFAOYSA-N 2-bromobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1Br XRXMNWGCKISMOH-UHFFFAOYSA-N 0.000 claims description 4
- NSTREUWFTAOOKS-UHFFFAOYSA-N 2-fluorobenzoic acid Chemical group OC(=O)C1=CC=CC=C1F NSTREUWFTAOOKS-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- IKCLCGXPQILATA-UHFFFAOYSA-N 2-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1Cl IKCLCGXPQILATA-UHFFFAOYSA-N 0.000 claims description 2
- CGMMPMYKMDITEA-UHFFFAOYSA-N 2-ethylbenzoic acid Chemical compound CCC1=CC=CC=C1C(O)=O CGMMPMYKMDITEA-UHFFFAOYSA-N 0.000 claims description 2
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- OSCVBYCJUSOYPN-UHFFFAOYSA-K ytterbium(3+);triacetate Chemical compound [Yb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OSCVBYCJUSOYPN-UHFFFAOYSA-K 0.000 claims description 2
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 claims description 2
- CKLHRQNQYIJFFX-UHFFFAOYSA-K ytterbium(III) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Yb+3] CKLHRQNQYIJFFX-UHFFFAOYSA-K 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 abstract description 8
- 239000001301 oxygen Substances 0.000 abstract description 8
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 239000012621 metal-organic framework Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 229910021529 ammonia Inorganic materials 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 229910052691 Erbium Inorganic materials 0.000 abstract description 2
- 229910052688 Gadolinium Inorganic materials 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 229910052727 yttrium Inorganic materials 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract 3
- 239000000243 solution Substances 0.000 description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- 239000011162 core material Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- -1 salt zirconium nitrate Chemical class 0.000 description 3
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 3
- 238000005211 surface analysis Methods 0.000 description 3
- 238000002076 thermal analysis method Methods 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- YSZKOFNTXPLTCU-UHFFFAOYSA-N barium lithium Chemical compound [Li].[Ba] YSZKOFNTXPLTCU-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- DBUHPIKTDUMWTR-UHFFFAOYSA-K erbium(3+);triacetate Chemical compound [Er+3].CC([O-])=O.CC([O-])=O.CC([O-])=O DBUHPIKTDUMWTR-UHFFFAOYSA-K 0.000 description 1
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 description 1
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- NFSAPTWLWWYADB-UHFFFAOYSA-N n,n-dimethyl-1-phenylethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=CC=C1 NFSAPTWLWWYADB-UHFFFAOYSA-N 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明涉及一种用作真空隔热板吸气剂的微孔金属有机框架材料及其合成方法，具有如下结构通式：M6(μ3‑OH)8Lx，式中M为Zr，Yb，Er，Gd，Y，Ti，L为2，5‑二甲基对苯二甲酸，2，5‑二乙基对苯二甲酸，3，5‑二甲基对苯二甲酸，3，5‑二乙氧基对苯二甲酸，[2,2'‑联吡啶]‑5,5'‑二甲酸，2',5'‑二甲基‑[1,1':4',1”‑三联苯]‑4,4”‑二羧酸，2',5'‑二丙基‑[1,1':4',1”‑三联苯]‑4,4”‑二羧酸，2',5'‑二甲氧基‑[1,1':4',1”‑三联苯]‑4,4”‑二羧酸，x＝6，9或12。该金属有机框架材料结晶程度高，晶体尺寸在纳米尺度，稳定性好，并具有合成工艺简单，产率较高等优点。该微孔金属有机框架材料的比表面积大，导热系数低，且对氨气、氧气、氮气、甲醛、水蒸气具有很强的吸附能力，可以用作真空隔热板中的吸气剂使用。The invention relates to a microporous metal-organic framework material used as a getter for a vacuum insulation panel and a synthesis method thereof, and has the following general structural formula: M 6 (μ 3 OH) 8 Lx, wherein M is Zr, Yb , Er, Gd, Y, Ti, L is 2,5-dimethylterephthalic acid, 2,5-diethylterephthalic acid, 3,5-dimethylterephthalic acid, 3,5 -diethoxyterephthalic acid, [2,2'-bipyridine]-5,5'-dicarboxylic acid, 2',5'-dimethyl-[1,1':4',1"- Terphenyl]-4,4"-dicarboxylic acid, 2',5'-dipropyl-[1,1':4',1"-terphenyl]-4,4"-dicarboxylic acid, 2',5'-dimethoxy-[1,1':4',1"-terphenyl]-4,4"-dicarboxylic acid, x=6, 9 or 12. The metal-organic framework material has high crystallinity, nanoscale crystal size, good stability, simple synthesis process, high yield and the like. The microporous metal organic framework material has large specific surface area, low thermal conductivity, and has strong adsorption capacity for ammonia, oxygen, nitrogen, formaldehyde and water vapor, and can be used as a getter in a vacuum heat insulation panel.
Description
Technical Field
The invention relates to a microporous metal organic framework material used as a getter of a vacuum insulation board and a synthesis method thereof.
Background
The vacuum heat insulation board is a novel high-efficiency heat insulation material, is prepared by filling a porous core material, wrapping the porous core material by using an air barrier film and then vacuumizing the air barrier film, and can effectively avoid heat transfer caused by air convection by utilizing the vacuum heat insulation principle, so that the heat conductivity coefficient can be greatly reduced. In the past, the vacuum insulation panel is mainly applied to the fields of military and national defense and the like, and along with the commercialization and cost reduction of the vacuum insulation panel, the vacuum insulation panel has been widely applied to the fields of refrigerators, freezers, electric water heaters, vending machines, freezers, refrigerated containers, heat transmission pipelines, nuclear power facilities, building wall insulation and the like. Compared with other heat-insulating materials, the vacuum heat-insulating plate has low heat conductivity coefficient, has the advantages of thin thickness, small volume and light weight of the heat-insulating layer when the heat-insulating technical requirements are the same, and is suitable for products with higher energy-saving requirements. In the long-term use process of the vacuum heat insulation plate, external air and moisture can gradually permeate into the heat insulation plate along with the time, and in addition, the filled core material can slowly release some gas, so that the vacuum degree is continuously reduced, the heat insulation performance is reduced, and the service life of a product is ended. In order to solve this problem, it is usually necessary to add a getter to absorb these gases, so that the insulation board can maintain a high degree of vacuum and maintain a low thermal conductivity, and finally, the service life of the vacuum insulation board is prolonged. Therefore, the good and bad adsorption performance of the getter is very important for improving the practical service life of the heat insulation plate. At present, the commonly used getters mainly comprise calcium oxide, iron powder, barium-lithium alloy and the like, however, the getters have limited adsorption capacity to gas and water vapor, and the heat conductivity coefficient is generally higher than that of a filled core material, so that the heat insulation effect of the getter position in the prepared heat insulation board is the worst. Compared with the traditional porous material, the microporous metal organic framework material has the advantages of large specific surface area, large adsorption capacity, low heat conductivity coefficient and the like, and is expected to replace the traditional getter to be applied to a heat insulation board.
Disclosure of Invention
The invention aims to provide a microporous metal organic framework material used as a getter of a vacuum insulation board, which has the following structural general formula: m6(μ3-OH)8Lx, wherein M is Zr, Yb, Er, Gd, Y and Ti, L is 2, 5-dimethyl terephthalic acid, 2, 5-diethyl terephthalic acid, 3, 5-dimethyl terephthalic acid, 3, 5-diethoxy terephthalic acid and [2,2' -bipyridyl]5,5 '-dicarboxylic acid, 2',5 '-dimethyl- [1,1':4',1' -terphenyl]-4,4 "-dicarboxylic acid, 2',5' -dipropyl- [1,1':4', 1" -terphenyl]-4,4 "-dicarboxylic acid, 2',5' -dimethoxy- [1,1':4', 1" -terphenyl]-4,4 "-dicarboxylic acid, x ═ 6, 9 or 12. The invention relates to a method for synthesizing a microporous metal organic framework material, which comprises the following steps:
(1) mixing the metal salt containing M and the organic ligand L according to the ratio of 1: 1-4, mixing and dissolving in water or an organic solvent to prepare a solution;
(2) adding a template agent into the solution and uniformly stirring, wherein the ratio of the organic ligand L to the template agent is 1: 1;
(3) and adding acid accounting for 1-6% of the total volume of the solution into the solution, uniformly stirring, putting into a closed hydrothermal kettle, reacting at a constant temperature of 70-150 ℃ for 2-8 days, naturally cooling to room temperature, performing centrifugal separation, and cleaning to obtain the microporous metal organic framework material.
The metal salt containing M in the synthesis method is zirconium nitrate, zirconium chloride, zirconium acetate, ytterbium nitrate, ytterbium acetate, ytterbium chloride, erbium nitrate, erbium chloride, erbium acetate, gadolinium nitrate, yttrium acetate, titanium nitrate and titanium chloride; the organic ligand L is 2, 5-dimethyl terephthalic acid, 2, 5-diethyl terephthalic acid, 3, 5-dimethyl terephthalic acid, 3, 5-diethoxy terephthalic acid, [2,2 '-bipyridyl ] -5,5' -dicarboxylic acid, 2',5' -dimethyl- [1,1':4',1 '-terphenyl ] -4,4' -dicarboxylic acid, 2',5' -dipropyl- [1,1':4',1 '-terphenyl ] -4,4' -dicarboxylic acid, 2',5' -dimethoxy- [1,1':4',1 '-terphenyl ] -4,4' -dicarboxylic acid; the organic solvent is any one or a mixture of several of N, N-dimethylformamide, N-dimethylacetamide, N-diethylacetamide, dimethyl sulfoxide, ethanol, dioxane and tetrahydrofuran according to any ratio; the template agent is o-fluorobenzoic acid, o-chlorobenzoic acid, o-bromobenzoic acid, o-methylbenzoic acid and o-ethylbenzoic acid; the acid is hydrochloric acid, nitric acid, acetic acid and tetrafluoroboric acid.
The invention has the beneficial effects that:
1. the microporous metal organic framework material has the advantages of high crystallization degree, nano-scale crystal size, simple synthesis process, high yield and the like, contains multi-core metal oxygen clusters, is connected with ligands to form various three-dimensional hole cage structures such as octahedrons and tetrahedrons, and has the pore channel size of 0.1-1 nm.
2. The metal organic framework material has excellent thermal stability and chemical stability, and can stably exist in water and various organic solvents such as N, N-dimethylformamide, N-dimethylacetamide, N-diethylacetamide, acetonitrile, ethanol, methanol, dimethyl sulfoxide, dioxane, tetrahydrofuran and the like.
3. The metal organic framework material has large specific surface area which is 4000m2More than g, the thermal conductivity coefficient is lower than 0.01 w/m.k, the problem of high thermal conductivity coefficient of the traditional getter is solved, the thermal decomposition temperature is more than 300 ℃, and the thermal stability is good.
4. The metal organic framework material has exposed active sites such as nitrogen atoms, can form strong interaction with nitrogen, oxygen, ammonia gas, carbon dioxide, water vapor and the like, has good adsorption capacity on gas, can replace the traditional getter to be applied to the vacuum heat insulation plate, and can replace the traditional polyurethane to be used as a refrigerator heat insulation material, so that the power consumption of a refrigerator can be reduced to 40-60% of the original power consumption.
Detailed Description
Example 1:
m is Zr, L is 2',5' -dimethoxy- [1,1':4',1 '-terphenyl ] -4,4' -dicarboxylic acid, x is 6. The synthesis method of the microporous metal organic framework material comprises the following steps:
(1) zr-containing metal salt zirconium nitrate and 2',5' -dimethoxy- [1,1':4',1 '-terphenyl ] -4,4' -dicarboxylic acid are mixed according to the weight ratio of 1: 1, mixing and dissolving in water to prepare a solution;
(2) adding o-methylbenzoic acid into the aqueous solution and uniformly stirring, wherein the ratio of 2',5' -dimethoxy- [1,1':4',1 '-terphenyl ] -4,4' -dicarboxylic acid to o-methylbenzoic acid is 1: 1;
(3) adding hydrochloric acid accounting for 1% of the total volume of the solution into the solution, uniformly stirring, putting into a closed hydrothermal kettle, reacting at a constant temperature of 150 ℃ for 2 days, naturally cooling to room temperature, performing centrifugal separation, and cleaning to obtain the microporous metal organic framework material.
The structure and performance of the product are characterized and confirmed by methods such as single crystal X-ray diffraction, element analysis, infrared spectrum, BET specific surface analysis, thermal analysis and the like, the obtained metal organic framework material belongs to a cubic system, the space group is Fm-3m, and a hexanuclear metal oxygen cluster is taken as a node and an organic ligand 2',5' -dimethoxy- [1,1':4',1' -terphenyl]The 4,4' -dicarboxylic acid is connected to form a space network and contains octahedral and tetrahedral two-hole cage structures, wherein the diameter of the octahedral hole cage is
The diameter of the tetrahedral pore cage is
The material has particle size of 50-200nm and specific surface area greater than 5000m2The thermal conductivity coefficient is lower than 0.01 w/m.k, the thermal decomposition temperature is higher than 350 ℃, and the getter has good adsorption capacity on nitrogen, oxygen, ammonia, carbon dioxide, water vapor and the like and can be used as a getter in a vacuum insulation board.
Example 2:
m is Yb, L is [2,2 '-bipyridine ] -5,5' -dicarboxylic acid, and x is 12. The synthesis method of the microporous metal organic framework material comprises the following steps:
(1) yb-containing metal salt ytterbium chloride and [2,2 '-bipyridyl ] -5,5' -dicarboxylic acid are mixed according to the proportion of 1: 4, mixing and dissolving in N, N-dimethylacetamide to prepare a solution;
(2) adding o-bromobenzoic acid into the solution and stirring uniformly, wherein the ratio of 2',5' -dimethoxy- [1,1':4',1 '-terphenyl ] -4,4' -dicarboxylic acid to o-bromobenzoic acid is 1: 1;
(3) adding tetrafluoroboric acid accounting for 6 percent of the total volume of the solution into the solution, uniformly stirring, putting the mixture into a closed hydrothermal kettle, reacting at a constant temperature of 150 ℃ for 8 days, naturally cooling to room temperature, performing centrifugal separation, and cleaning to obtain the microporous metal organic framework material.
The structure and performance of the product are characterized and confirmed by methods such as single crystal X-ray diffraction, element analysis, infrared spectrum, BET specific surface analysis, thermal analysis and the like, the obtained metal organic framework material belongs to a cubic system, the space group is Fm-3m, and a trinuclear metal oxygen cluster is taken as a node and an organic ligand [2,2' -bipyridine ]]The connection of the 5,5' -dicarboxylic acid forms a space network, the particle size of the material is 100-500nm, and the specific surface area is more than 4000m2The thermal conductivity coefficient is lower than 0.01 w/m.k, the thermal decomposition temperature is higher than 380 ℃, and the ligand contains nitrogen atoms as active sites, so that the interaction with nitrogen, oxygen, ammonia, carbon dioxide and water vapor can be enhanced, the gas adsorption capacity is excellent, and the getter can be used as a getter in a vacuum insulation board.
Example 3:
m is Ti, L is 3, 5-diethoxyterephthalic acid, and x is 6. The synthesis method of the microporous metal organic framework material comprises the following steps:
(1) mixing metal salt titanium nitrate containing Ti and 3, 5-diethoxy terephthalic acid according to the weight ratio of 1: 2 is mixed and dissolved in a mixed solvent of ethanol and N, N-dimethylformamide to prepare a solution;
(2) adding o-fluorobenzoic acid into the solution and stirring uniformly, wherein the ratio of the 3, 5-diethoxyterephthalic acid to the o-fluorobenzoic acid is 1: 1;
(3) adding nitric acid with the volume being 2% of the total volume of the solution into the solution, uniformly stirring, putting the solution into a closed hydrothermal kettle, reacting for 4 days at a constant temperature of 130 ℃, naturally cooling to room temperature, performing centrifugal separation, and cleaning to obtain the microporous metal organic framework material.
By passingThe structure and performance of the product are characterized and confirmed by methods such as single crystal X-ray diffraction, element analysis, infrared spectrum, BET specific surface analysis, thermal analysis and the like, the obtained metal organic framework material belongs to a cubic crystal system, the space group is Fm-3m, a hexanuclear metal oxygen cluster is used as a node to be connected with organic ligand 3, 5-diethoxy terephthalic acid to form a space network, the particle size of the material is 50-400nm, and the specific surface area is more than 5000m2The thermal conductivity coefficient is lower than 0.01 w/m.k, the thermal decomposition temperature is higher than 320 ℃, and the getter has excellent gas adsorption capacity on nitrogen, oxygen, ammonia, carbon dioxide and water vapor and can be used as a getter in a vacuum insulation board.
Claims (4)
1. The vacuum insulation panel comprises a getter, and is characterized in that the getter adopts a microporous metal organic framework material, and the microporous metal organic framework material has the following structural general formula: m6(μ3-OH)8Lx, wherein M is Zr, Yb or Ti, L is 2, 5-dimethyl terephthalic acid, 2, 5-diethyl terephthalic acid, 3, 5-dimethyl terephthalic acid, 3, 5-diethoxy terephthalic acid and [2,2' -bipyridyl]5,5' -dicarboxylic acid, 2',5' -dimethyl- [1,1':4',1' ' -terphenyl]-4,4 "-dicarboxylic acid, 2',5' -dipropyl- [1,1':4', 1" -terphenyl]-4,4 "-dicarboxylic acid or 2',5' -dimethoxy- [1,1':4', 1" -terphenyl]-4,4 "-dicarboxylic acid, x ═ 6, 9, or 12; the synthesis method of the microporous metal organic framework material comprises the following steps:
(1) mixing the metal salt containing M and the organic ligand L according to the ratio of 1: 1-4, mixing and dissolving in water or an organic solvent to prepare a solution;
(2) adding a template agent into the solution and uniformly stirring, wherein the molar ratio of the organic ligand L to the template agent is 1: 1; the template agent is o-fluorobenzoic acid, o-chlorobenzoic acid, o-bromobenzoic acid, o-methylbenzoic acid or o-ethylbenzoic acid;
(3) adding acid accounting for 1-6% of the total volume of the solution into the solution, uniformly stirring, putting the solution into a closed hydrothermal kettle, and heating the kettle to 70-150 DEG CoC, reacting at constant temperature for 2-8 days, naturally cooling to room temperature, centrifugally separating, and cleaningObtaining the microporous metal organic framework material.
2. The vacuum insulation panel according to claim 1, wherein the M-containing metal salt of step (1) is zirconium nitrate, zirconium chloride, zirconium acetate, ytterbium nitrate, ytterbium acetate, ytterbium chloride, titanium nitrate, or titanium chloride.
3. The vacuum insulation panel according to claim 1, wherein the organic solvent in step (1) isN, N-dimethylformamide,N,N-dimethylacetamide,N,NAny one or more of diethylacetamide, dimethyl sulfoxide, ethanol, dioxane and tetrahydrofuran is mixed according to any ratio.
4. The vacuum insulation panel according to claim 1, wherein the acid of step (3) is hydrochloric acid, nitric acid, acetic acid or tetrafluoroboric acid.
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