CN109876775B - Metal organic framework fiber material and preparation method thereof - Google Patents
Metal organic framework fiber material and preparation method thereof Download PDFInfo
- Publication number
- CN109876775B CN109876775B CN201711279609.7A CN201711279609A CN109876775B CN 109876775 B CN109876775 B CN 109876775B CN 201711279609 A CN201711279609 A CN 201711279609A CN 109876775 B CN109876775 B CN 109876775B
- Authority
- CN
- China
- Prior art keywords
- organic polymer
- polymer fiber
- solution
- copper salt
- trimesic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 75
- 239000002657 fibrous material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000835 fiber Substances 0.000 claims abstract description 91
- 229920000620 organic polymer Polymers 0.000 claims abstract description 85
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000000243 solution Substances 0.000 claims abstract description 55
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000013148 Cu-BTC MOF Substances 0.000 claims abstract description 48
- 150000001879 copper Chemical class 0.000 claims abstract description 39
- 239000013078 crystal Substances 0.000 claims abstract description 39
- 238000009987 spinning Methods 0.000 claims abstract description 33
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 238000002791 soaking Methods 0.000 claims abstract description 23
- 238000001179 sorption measurement Methods 0.000 claims abstract description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 19
- 239000011261 inert gas Substances 0.000 claims abstract description 13
- 239000012266 salt solution Substances 0.000 claims abstract description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005977 Ethylene Substances 0.000 claims abstract description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 11
- 150000001408 amides Chemical class 0.000 claims abstract description 10
- 238000007598 dipping method Methods 0.000 claims abstract description 9
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 8
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000000967 suction filtration Methods 0.000 claims abstract 2
- 239000000463 material Substances 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 38
- QCIDBNKTKNBPKM-UHFFFAOYSA-N dihydroxybenzamide Natural products NC(=O)C1=CC=CC(O)=C1O QCIDBNKTKNBPKM-UHFFFAOYSA-N 0.000 claims description 20
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 14
- 239000001307 helium Substances 0.000 claims description 14
- 229910052734 helium Inorganic materials 0.000 claims description 14
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 9
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- BBGVVPLPLBJJLS-UHFFFAOYSA-N copper ethanol dinitrate Chemical compound C(C)O.[N+](=O)([O-])[O-].[Cu+2].[N+](=O)([O-])[O-] BBGVVPLPLBJJLS-UHFFFAOYSA-N 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- NMFFUUFPJJOWHK-UHFFFAOYSA-N 2-phenoxyaniline Chemical compound NC1=CC=CC=C1OC1=CC=CC=C1 NMFFUUFPJJOWHK-UHFFFAOYSA-N 0.000 claims description 3
- GZTBKEOTCAVWNJ-UHFFFAOYSA-L C(C)O.C(C)(=O)[O-].[Cu+2].C(C)(=O)[O-] Chemical compound C(C)O.C(C)(=O)[O-].[Cu+2].C(C)(=O)[O-] GZTBKEOTCAVWNJ-UHFFFAOYSA-L 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 claims description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- MWTXLMFPCZIOHL-UHFFFAOYSA-L S(=O)(=O)([O-])[O-].[Cu+2].C(C)O Chemical compound S(=O)(=O)([O-])[O-].[Cu+2].C(C)O MWTXLMFPCZIOHL-UHFFFAOYSA-L 0.000 claims description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 238000009423 ventilation Methods 0.000 claims description 2
- 125000006160 pyromellitic dianhydride group Chemical group 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 17
- 239000013084 copper-based metal-organic framework Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 10
- -1 and the like Chemical compound 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 230000000844 anti-bacterial effect Effects 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- VHKFFPOTSWQHPK-UHFFFAOYSA-N C(C)O.C1(=CC(=CC(=C1)C(=O)O)C(=O)O)C(=O)O Chemical compound C(C)O.C1(=CC(=CC(=C1)C(=O)O)C(=O)O)C(=O)O VHKFFPOTSWQHPK-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000002121 nanofiber Substances 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000012924 metal-organic framework composite Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- 239000013255 MILs Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- SCGJLFGXXZTXSX-UHFFFAOYSA-N copper;ethanol Chemical compound [Cu].CCO SCGJLFGXXZTXSX-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000013259 porous coordination polymer Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
Images
Landscapes
- Artificial Filaments (AREA)
Abstract
The invention relates to a metal organic framework fiber material and a preparation method thereof, which comprises the steps of firstly mixing acid anhydride, ether reagent and amide in proportion, introducing inert gas to prepare spinning solution, and obtaining organic polymer fiber through electrostatic spinning; then, dipping the organic polymer fiber in a copper salt solution, taking out the organic polymer fiber, placing the organic polymer fiber in a trimesic acid solution, then placing the organic polymer fiber in ethanol, taking out the organic polymer fiber, drying the organic polymer fiber, and repeatedly dipping the organic polymer fiber to obtain HKUST-1 seed crystal/organic polymer fiber; and then heating the HKUST-1 seed crystal/organic polymer fiber, taking out, soaking in a solution containing copper salt and trimesic acid, heating in a sealed state, taking out, and performing suction filtration, washing and drying to obtain the metal organic framework fiber material. In the fiber material prepared by the invention, the HKUST-1 grows uniformly and is tightly combined with the organic polymer fiber, so that the HKUST-1 is prevented from falling off, the service cycle is prolonged, and the ethylene/nitrogen adsorption separation effect is higher.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a metal organic framework fiber material and a preparation method thereof.
Background
Metal-Organic Framework Materials (MOFs), also known as porous coordination polymers, are a class of porous coordination materials that have emerged in recent years by self-assembly. The catalyst has the advantages of large specific surface area, easy regulation of pore size, strong selective coordination and the like, and is widely applied to the technical fields of gas adsorption separation, homogeneous catalytic reaction, medicine and conduction transmission. Copper-based metal-organic framework material HKUST-1 is an important metal-organic framework material and is one of the few metal-organic framework materials which are commercially produced so far. The difficulty restricting the large-scale application of the HKUST-1 is the molding technology of the material, and the HKUST-1 crystal structure is brittle and easy to crack in the extrusion molding process, so people shift the research to load molding.
Compared with inorganic carriers, the organic polymer carrier has advantages in the aspects of shape plasticity, material flexibility, material surface property and the like; by the electrostatic spinning technology, the organic polymer fiber carrier with nanometer size can be obtained, which is beneficial to loading metal organic framework materials and is used for various reactions including gas adsorption storage and separation.
CN105854853A discloses a preparation method of an antibacterial metal organic framework composite nanofiber. According to the method, silver metal organic framework nano particles are subjected to particle surface modification through an auxiliary agent, and are blended with a high molecular polymer in a solvent to obtain a raw material solution, and then the composite nano fibers are prepared by utilizing an electrostatic spinning technology. The composite nanofiber has good structural stability, and can control the release concentration and speed of metal ions. However, the composite nanofiber material obtained by the method has limited metal organic framework material load, and the metal organic framework material particles have uneven sizes, so that the adsorption, catalysis and other action effects are influenced; in addition, various polymer prepolymer components added into the metal-organic framework material dispersion liquid can easily cause the metal-organic framework material to be coated in the dispersion liquid or cause structural damage, and the physicochemical properties of the metal-organic framework material are also influenced.
CN106120015A discloses a copper-based metal organic framework antibacterial fiber, which is prepared from polyester, a copper-based metal organic framework material and an antibacterial agent, wherein the polyester accounts for 80-99.9%, and the copper-based metal organic framework material accounts for 0.1-20%. The preparation method comprises the steps of carrying out melt spinning on the copper-based metal organic framework material and polyester through a spinning machine to obtain the copper-based metal organic framework polyester composite fiber; and (3) soaking the copper-based metal organic framework polyester composite fiber in an antibacterial agent, rinsing and drying to obtain the copper-based metal organic framework antibacterial fiber. The copper-based metal organic framework antibacterial fiber is simple in preparation method and has a good antibacterial effect. However, the copper-based metal organic framework antibacterial fiber has low content of metal organic framework materials, and the polyester selected as the organic polymer carrier has poor compatibility with the metal organic framework materials, so that the copper-based metal organic framework antibacterial fiber is not beneficial to long-term use.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a metal organic framework fiber material and a preparation method thereof, and particularly provides a fiber material compounded by the metal organic framework material and organic polymer fibers and a preparation method thereof. In the composite fiber material, the HKUST-1 grows uniformly and is tightly combined with the organic polymer fibers, so that the HKUST-1 is prevented from falling off, the service cycle is prolonged, and the composite fiber material has a high ethylene/nitrogen adsorption separation effect.
The preparation method of the metal organic framework fiber material provided by the invention comprises the following steps:
(1) mixing anhydride, ether reagent and amide in proportion, introducing inert gas to prepare spinning solution, and obtaining organic polymer fiber through electrostatic spinning;
(2) soaking the organic polymer fiber in a copper salt solution, taking out the organic polymer fiber, placing the organic polymer fiber in a trimesic acid solution, then placing the organic polymer fiber in ethanol for soaking, taking out the organic polymer fiber, drying the organic polymer fiber, and repeatedly soaking to obtain HKUST-1 seed crystal/organic polymer fiber;
(3) heating the HKUST-1 seed crystal/organic polymer fiber, taking out, soaking in a solution containing copper salt and trimesic acid, sealing, heating for reaction, taking out, vacuum-filtering, washing, and drying to obtain the metal organic framework fiber material.
In the step (1), the acid anhydride is at least one selected from phthalic anhydride, maleic anhydride, pyromellitic dianhydride, trimellitic anhydride, and the like, and pyromellitic dianhydride is preferred. The ether reagent is at least one selected from 2-aminodiphenyl ether, 3,4 ' -diaminodiphenyl ether, 4 ' -diaminodiphenyl ether, etc., preferably 3,4 ' -diaminodiphenyl ether. The amide is at least one selected from dimethylformamide, dimethylacetamide, formamide, methylacetamide, dihydroxybenzamide, and the like, and dihydroxybenzamide is preferred. The mass ratio of the acid anhydride to the ether reagent to the amide is 1: (0.5-3.5): (5-30), preferably 1: (0.8-1.5): (8.5-15).
In the step (1), the inert gas is at least one selected from high-purity nitrogen, helium, argon and the like, the gas flow rate is 15 mL/min-35 mL/min, and the ventilation time is 3 h-7 h; the reaction temperature is-10 ℃ to 35 ℃, preferably-3 ℃ to 15 ℃, and the stirring speed is 150rpm to 300 rpm.
In the step (1), the organic polymer fiber obtained by electrostatic spinning has a diameter of 450nm to 550nm and a specific surface area of 35m2/g～65m2Per g, pore volume of 0.1cm3/g～0.3 cm3(ii) in terms of/g. The specific process of electrostatic spinning can be as follows: and (2) filling the spinning stock solution into an injector, installing a spinning nozzle, setting the sample injection speed of an injection pump to be 0.5-5 mL/h and the spinning distance to be 10-20 cm, starting a spinning receiving device, setting the rotating speed to be 100-150 rpm, setting the voltage to be 15-30 kV and the current to be 0.01-0.1 mA, spinning and collecting the organic polymer fiber.
In the step (2), the copper salt solution is preferably a copper salt ethanol solution, and may be at least one of a copper nitrate ethanol solution, a copper acetate ethanol solution, a copper sulfate ethanol solution and the like, and is preferably a copper nitrate ethanol solution. In the copper salt solution, the mass concentration of the copper salt is 0.1-5%, preferably 0.5-2%. The mass ratio of the organic polymer fiber to the copper salt is 1: (0.1 to 3), preferably 1: (0.5 to 1.5); the dipping time is 10 min-40 min.
In the step (2), the mass concentration of trimesic acid in the trimesic acid solution is 0.1-5%, preferably 0.5-2%; the dipping time is 30 min-100 min. The trimesic acid solution is preferably an ethanol solution of trimesic acid. The mass ratio of the organic polymer fibers to the trimesic acid is 1: (0.05 to 1.5), preferably 1: (0.25-0.75).
In the step (2), the material is soaked in ethanol for 1min to 10min, then taken out and dried, preferably under the protection of inert gas, the inert gas is at least one of high-purity nitrogen, helium, argon and the like, the drying temperature is 20 ℃ to 30 ℃, and the drying time is 5h to 10 h. The number of the repeated impregnation is 2 or more, preferably 10 to 20.
In the step (3), the HKUST-1 seed crystal/organic polymer fiber is transferred to a muffle furnace for heating treatment, wherein the treatment temperature is 200-400 ℃, and preferably 260-330 ℃; the heating rate is 1 to 10 ℃/min, preferably 3 to 6 ℃/min. The copper salt is selected from one or more of copper nitrate, copper acetate, copper sulfate and the like, and is preferably copper nitrate. In the solution containing copper salt and trimesic acid, the mass concentration of the copper salt is 1-20 percent, preferably 5-10 percent; the mass concentration of the trimesic acid is 1 to 20 percent, preferably 2.5 to 5 percent. In the solution containing copper salt and trimesic acid, the solvent is preferably ethanol and water, and the mass ratio of the ethanol to the water is 1: (0.5 to 3). The mass ratio of the HKUST-1 seed crystal/organic polymer fiber, the copper salt and the trimesic acid is 1: (1-15): (0.5 to 7.5), preferably 1: (5-10): (2.5-5); the dipping time is 10-20 h.
In the step (3), the heating temperature after sealing is 70-150 ℃, and the heating time is 8-15 h. Preferably, the washing is carried out by using an ethanol water solution, wherein the mass ratio of ethanol to water is 1: (0.5 to 3). The drying temperature is 50-200 ℃, and the drying time is 6-10 h; the drying is preferably performed under protection of an inert gas selected from at least one of high purity nitrogen, helium, argon, and the like.
The metal organic framework fiber material is prepared by the method. The specific surface area of the metal organic framework fiber material is 890m2/g～1050m2Per g, pore volume of 0.41cm3/g～0.6 cm3(iv) per gram, wherein the average particle diameter of the metal organic framework fiber material is 0.5 to 3.5 μm.
The metal organic framework fiber material prepared by the invention can be used for selective adsorption separation of light hydrocarbons such as ethylene/nitrogen, propylene/nitrogen, ethane/nitrogen and the like and nitrogen. Under 273-293K and 0.1-2atm, the separation coefficient of ethylene/nitrogen is 6-10.
Compared with the prior art, the invention has the following advantages:
(1) the organic polymer fiber synthesized by the method is rich in carboxyl, and is beneficial to the growth of the HKUST-1 seed crystal and the HKUST-1 metal organic framework material on the organic polymer fiber, so that the organic polymer fiber is firmly and fixedly carried on a carrier, the service performance of the material can be obviously improved, and the service cycle can be prolonged.
(2) The invention synthesizes the metal organic framework fiber material by adopting a mode of pre-preparing the HKUST-1 seed crystal/organic polymer fiber, and the induction effect of the HKUST-1 seed crystal can effectively shorten the growth time of the HKUST-1 metal organic framework material and improve the growth density, thereby being beneficial to improving the adsorption and separation effects of the HKUST-1 metal organic framework material.
(3) According to the invention, the organic polymer fibers are soaked in a copper salt solution, taken out and placed in a trimesic acid solution, and then the soaked materials are placed in ethanol for repeated soaking, so that the control of HKUST-1 seed crystals and the crystal size of the HKUST-1 metal organic framework material is facilitated, the HKUST-1 metal organic framework material obtains more adsorption active sites, and the adsorption separation effect is facilitated to be improved.
(4) Firstly, pre-growing an HKUST-1 crystal seed on organic polymer fibers to enable the crystal seed to be firmly and fixedly carried on a carrier, and then, carrying out temperature programming treatment to enable part of the crystal seed to grow on the surface of the carrier and develop the HKUST-1 crystal with a complete crystal nucleus structure; and then the crystal is immersed into a copper salt-containing trimesic acid solution to promote the growth of the rest seed crystals on the surface and inside the carrier, increase the loading capacity of the HKUST-1 crystal on the carrier, prevent the HKUST-1 metal organic framework material from falling off and improve the service cycle.
Drawings
Fig. 1 to 5 are Scanning Electron Micrographs (SEM) of the organic polymer fibers, and the metal-organic framework fiber materials of example 1, example 6, comparative example 5, and comparative example 12.
Detailed Description
The following examples further illustrate the preparation and effects of the metal organic framework fiber material of the present invention. The embodiments are implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited by the following embodiments.
The experimental procedures in the following examples are, unless otherwise specified, conventional in the art. The experimental materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified.
Example 1
6.54g of pyromellitic dianhydride, 6g of 3, 4' -diaminodiphenyl ether and 70g of dihydroxybenzamide were weighed, helium gas was introduced at 20mL/min, and the mixture was stirred at 1 ℃ and 200rpm for 5 hours to obtain a spinning dope. Loading the spinning solution into an injector, installing a spinning nozzle, setting the sample injection speed of an injection pump to be 1.5mL/h and the spinning distance to be 12cm, starting a spinning receiving device, and rotating at the speed of 100rpm, setting the voltage to be 25kV and the current to be 0.03mA, starting spinning and collecting the organic polymer fibers. The obtained organic polymer fiber has a diameter of 500nm and a specific surface area of 35m2Per g, pore volume of 0.12cm3/g。
Soaking 1g of organic polymer fiber in 100g of 1% copper nitrate ethanol solution, taking out and soaking in 50g of 1% trimesic acid ethanol solution after 25min, taking out and soaking in ethanol after 50min, taking out and drying at 25 ℃ for 6h under the protection of helium after 10 min. The impregnation was repeated a total of 5 times in the above manner to obtain HKUST-1 seed/organic polymer fibers. Transferring the HKUST-1 seed crystal/organic polymer fiber to a muffle furnace for heating treatment, wherein the treatment temperature and the heating rate are respectively 300 ℃ and 5 ℃/min.
Taking 1g of HKUST-1 seed crystal/organic polymer fiber subjected to temperature rise treatment, and soaking the HKUST-1 seed crystal/organic polymer fiber into 100g of 10 mass percent cupric nitrate and 5 mass percent trimesic acid ethanol solution, wherein the mass ratio of ethanol to deionized water is 1: 1, the dipping time is 10 h; then transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, and heating the reaction kettle at 90 ℃ for reaction for 10 hours. Taking out the product, and mixing the product with a mass ratio of 1: 1, washing with ethanol aqueous solution, and drying for 6h under the protection of helium, wherein the treatment temperature is 150 ℃, so as to obtain the metal organic framework fiber material A.
Example 2
The same as example 1, except that phthalic anhydride was used instead of pyromellitic dianhydride, and other reaction conditions and material compositions were unchanged, the metal-organic framework fiber material B was obtained.
Example 3
The same as example 1, except that maleic anhydride was used instead of pyromellitic dianhydride, and other reaction conditions and material compositions were unchanged, the metal organic framework fiber material C was obtained.
Example 4
The same as example 1, except that trimellitic anhydride was used in place of pyromellitic dianhydride, and other reaction conditions and material compositions were not changed, the metal organic framework fiber material D was obtained.
Example 5
The same as example 1, except that 2-aminodiphenyl ether was used in place of 3, 4' -diaminodiphenyl ether, and other reaction conditions and material compositions were unchanged, the metal-organic framework fiber material E was obtained.
Example 6
The same as example 1, except that 4,4 '-diaminodiphenyl ether was used in place of 3, 4' -diaminodiphenyl ether, and other reaction conditions and material compositions were unchanged, the metal-organic framework fiber material F was obtained.
Example 7
The same as example 1, except that dimethylformamide was used instead of dihydroxybenzamide, and other reaction conditions and material compositions were not changed, the metal organic framework fiber material G was obtained.
Example 8
The same as example 1, except that formamide was used instead of dihydroxybenzamide, and other reaction conditions and material compositions were unchanged, the metal organic framework fiber material H was obtained.
Example 9
The same as example 1, except that methyl acetamide was used instead of dihydroxybenzamide, and other reaction conditions and material compositions were unchanged, the metal organic framework fiber material I was obtained.
Example 10
The same as example 1, except that the copper salt solution was replaced with the copper acetate ethanol solution, and other reaction conditions and material compositions were unchanged, the metal organic framework fiber material J was obtained.
Example 11
The same as example 1, except that copper sulfate ethanol solution was used instead of copper nitrate ethanol solution in copper salt solution, and other reaction conditions and material composition were not changed, the metal organic framework fiber material K was obtained.
Example 12
The same as example 1, except that copper sulfate was used instead of copper nitrate in the solution containing copper salt and trimesic acid, and other reaction conditions and material compositions were not changed, the metal organic framework fiber material L was obtained.
Example 13
The same as example 1, except that copper acetate was used instead of copper nitrate in the solution containing copper salt and trimesic acid, and other reaction conditions and material compositions were unchanged, the metal organic framework fiber material M was obtained.
Example 14
6.54g of pyromellitic dianhydride, 9.81g of 3, 4' -diaminodiphenyl ether and 98.1g of dihydroxybenzamide were weighed, and helium gas was introduced at 35mL/min, and stirred at 15 ℃ and 300rpm for 7 hours to obtain a spinning dope. And (3) filling the spinning stock solution into an injector, installing a spinning nozzle, setting the sample injection speed of an injection pump to be 5mL/h and the spinning distance to be 20cm, starting a spinning receiving device, setting the rotating speed to be 150rpm, setting the voltage to be 30kV and the current to be 0.1mA, starting spinning and collecting the organic polymer fibers. The obtained organic polymer fiber has a diameter of 550nm and a specific surface area of 65m2Per g, pore volume of 0.3cm3/g。
Soaking 1g of organic polymer fiber in 75g of 2% copper nitrate ethanol solution, taking out and soaking in 37.5g of 2% trimesic acid ethanol solution after 40min, taking out and soaking in ethanol after 100min, taking out and drying at 30 ℃ for 10h under the protection of helium after 10 min. The impregnation was repeated a total of 20 times in the above manner to obtain HKUST-1 seed/organic polymer fibers. Transferring the HKUST-1 seed crystal/organic polymer fiber to a muffle furnace for heating treatment, wherein the treatment temperature and the heating rate are 330 ℃ and 6 ℃/min respectively.
Taking 1g of HKUST-1 seed crystal/organic polymer fiber subjected to temperature rise treatment, and soaking the HKUST-1 seed crystal/organic polymer fiber into 100g of aqueous solution of copper nitrate with the mass concentration of 10% and trimesic acid ethanol with the mass concentration of 5%, wherein the mass ratio of ethanol to deionized water is 1: 3, the dipping time is 20 h; then transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, and heating the reaction kettle at 150 ℃ for reaction for 15 hours. Taking out the product, and mixing the product with a mass ratio of 1: 3, washing with an ethanol aqueous solution, and drying for 10 hours under the protection of helium, wherein the treatment temperature is 200 ℃, so as to obtain the metal organic framework fiber material N.
Example 15
6.54g of pyromellitic dianhydride, 5.23g of 3, 4' -diaminodiphenyl ether and 55.59g of dihydroxybenzamide were weighed and weighed in 15 mL-Introducing helium gas in the mixture for min, and stirring the mixture for 3h at the temperature of minus 3 ℃ and 150rpm to obtain spinning stock solution. And (3) filling the spinning stock solution into an injector, installing a spinning nozzle, setting the sample injection speed of an injection pump to be 0.5mL/h and the spinning distance to be 10cm, starting a spinning receiving device, setting the rotating speed to be 100rpm and the voltage to be 15kV and the current to be 0.01mA, starting spinning and collecting the organic polymer fibers. The obtained organic polymer fiber has a diameter of 450nm and a specific surface area of 35m2Per g, pore volume of 0.1cm3/g。
Soaking 1g of organic polymer fiber in 100g of 0.5% copper nitrate ethanol solution, taking out and soaking in 50g of 0.5% trimesic acid ethanol solution after 10min, taking out and soaking in ethanol again after 50min, taking out and drying at 20 ℃ for 5h under the protection of helium after 10 min. The impregnation was repeated 10 times in total in the above manner to obtain HKUST-1 seed/organic polymer fibers. Transferring the HKUST-1 seed crystal/organic polymer fiber to a muffle furnace for heating treatment, wherein the treatment temperature and the heating rate are 260 ℃ and 3 ℃/min respectively.
Taking 1g of HKUST-1 seed crystal/organic polymer fiber subjected to temperature rise treatment, and soaking the seed crystal/organic polymer fiber into 100g of 5% copper nitrate and 2.5% trimesic acid ethanol aqueous solution, wherein the mass ratio of ethanol to deionized water is 1:0.5, the dipping time is 10 h; then transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, and heating the reaction kettle at 70 ℃ for reaction for 8 hours. Taking out the product, and mixing the product with a mass ratio of 1: washing with 0.5 of ethanol aqueous solution, and drying for 6h under the protection of helium, wherein the treatment temperature is 50 ℃, so as to obtain the metal organic framework fiber material O.
Comparative example 1
The same as example 1, except that a commercially available one having a diameter of 500nm and a specific surface area of 35m was used2Per g, pore volume of 0.12cm3The organic polymer fiber of the invention is replaced by the organic polymer fiber of the invention, other reaction conditions and material compositions are not changed, and the metal organic framework fiber material P is obtained.
Comparative example 2
The same as example 1, except that acid anhydride was omitted in the preparation of the organic polymer fiber, and other reaction conditions and material compositions were unchanged, the metal organic framework fiber material Q was obtained.
Comparative example 3
The same as example 1, except that ether reagent was omitted in the preparation of organic polymer fiber, and other reaction conditions and material composition were unchanged, to obtain the metal organic framework fiber material R.
Comparative example 4
The same as example 1, except that amide was omitted in the preparation of the organic polymer fiber, and other reaction conditions and material compositions were unchanged, the metal organic framework fiber material S was obtained.
Comparative example 5
The same as example 1, except that the inert gas is not introduced in the preparation of the organic polymer fiber, and other reaction conditions and material compositions are not changed, the metal organic framework fiber material T is obtained.
Comparative example 6
The same as example 1, except that the impregnated material was not impregnated in ethanol, and other reaction conditions and material compositions were unchanged, the metal organic framework fiber material U was obtained.
Comparative example 7
The same as example 1, except that the HKUST-1 seed crystal/organic polymer fiber was not heated, and other reaction conditions and material compositions were not changed, the metal organic framework fiber material V was obtained.
Comparative example 8
The difference of the method is that the HKUST-1 seed crystal/organic polymer fiber is not dipped in the solution containing the copper salt and the trimesic acid again, and other reaction conditions and material compositions are not changed to obtain the metal organic framework fiber material W as in the example 1.
Comparative example 9
The same as example 1, except that the HKUST-1 seed crystal/organic polymer fiber is not heated in a sealed manner after being impregnated, and other reaction conditions and material compositions are not changed, the metal organic framework fiber material X is obtained.
Comparative example 10
In the same manner as in example 1, the HKUST-1 seed crystal/organic polymer fiber synthesis step was omitted, and the organic polymer fiber obtained by electrospinning was directly immersed in a solution containing copper nitrate and trimesic acid without changing other conditions and material composition, to obtain a metal-organic framework fiber material Y.
Comparative example 11
The same as example 1, except that the solvents of the copper salt solution and the trimesic acid solution in the step (2) are acetone, and other reaction conditions and material compositions are unchanged, so as to obtain the metal organic framework fiber material Z.
Comparative example 12
According to the method described in CN105854853A, silver nitrate, 1,3, 5-trimesic acid and imidazole are placed in a reaction solvent to be mixed and stirred for 30min, a pH value regulator is used for regulating the pH value of the solution to 6-8 while stirring, and the solution is dried in vacuum at 50-80 ℃ to obtain the silver metal organic framework compound nano-particles. Under the action of ultrasonic waves and stirring, uniformly dispersing the auxiliary agent in a dichloromethane solution; and adding silver metal organic framework compound nano particles, and continuing to perform ultrasonic treatment and stirring until the particles are completely dispersed to obtain a mixed solution. Dissolving a high molecular polymer in a dichloromethane solvent to obtain a mixed solution, mixing the two mixed solutions according to a volume ratio of 1: 0.5-3, and stirring and mixing for 12 hours to obtain a spinning raw material solution. And finally, filling the spinning raw material liquid into an injector, starting spinning and collecting a sample to obtain the silver metal organic framework composite nanofiber A1.
Comparative example 13
According to the method described in CN106120015A, 0.1% of copper-based metal-organic framework material with levamil framework type (MILs) of 2000 mesh particle size, 99.9% of polyethylene terephthalate (PET) were melt-spun by a spinning machine to obtain a copper-based metal-organic framework polyester composite fiber a 2.
Test example 1
The physicochemical properties of the metal-organic framework fiber materials of examples 1 to 15 and comparative examples 1 to 13 were measured, and the specific results are shown in table 1. The BET specific surface area and the pore volume are measured by a low-temperature liquid nitrogen adsorption method, and the tester is an ASAP 2020 type adsorber of Micromeritics company in the United states. The ethylene/nitrogen separation coefficient was determined at 273K and 1bar using a Micromeritics HPVA-100 type adsorber. The particle diameter was measured by Shimadzu particle size Analyzer (SALD-2300) and the laser diffraction method was in accordance with International Standard ISO 13320/JIS Z8825-1.
TABLE 1 physicochemical Properties of the fiber materials prepared in examples and comparative examples
As can be seen from Table 1, the metal organic framework fiber material prepared by the method has good physicochemical properties, is suitable for selective adsorption and separation of ethylene/nitrogen, and the BET specific surface area, the pore volume and the ethylene/nitrogen separation coefficient of a sample A respectively reach 1050m2/g、0.6cm3G and 10. The organic polymer fiber carrier synthesized by the method is rich in carboxyl functional groups, is easy to immobilize electropositive transition metal ions, is beneficial to growth of HKUST-1 seed crystals and HKUST-1 metal organic framework materials on the organic polymer fiber carrier, and can prolong the service life of the materials. After 50 cycles of continuous adsorption-desorption, the ethylene/nitrogen separation coefficient of sample a remained at 9.97.
As can be seen from the electron micrographs in FIGS. 2 to 5, in the metal organic framework fiber material prepared by the method of the present invention, the metal organic framework material grown on the organic polymer fiber carrier has uniform and small particle diameter, and the average particle diameter of the metal organic framework material of sample A is 0.5 μm, which is beneficial to generating more adsorption active sites on the inner and outer surfaces of the particles, i.e., improving the adsorption separation effect of the mixed gas.
Test example 2
The adsorption separation effect of the metal organic framework fiber material of example 1 on different mixed gases was determined, the adsorption amount was determined by using a Micromeritics HPVA-100 type adsorption apparatus, the adsorption conditions were 273K and 1bar, before the sample test, a vacuum was first applied to the adsorption apparatus at 473K for 12h, the vacuum pressure was less than 10 μmHg, and then the specified pressure was reached under the guidance of the program pressure increasing module, and the test results are shown in Table 2.
Table 2 comparison of mixed gas adsorption separation effect of materials prepared in example 1
As can be seen from Table 2, the metal organic framework fiber material prepared by the invention is beneficial to the selective adsorption separation of light hydrocarbons such as ethylene/nitrogen, propylene/nitrogen, ethane/nitrogen and the like and nitrogen, in particular to the selective adsorption separation of ethylene/nitrogen, and the separation coefficient reaches 10.
Claims (27)
1. The preparation method of the metal organic framework fiber material is characterized by comprising the following steps:
(1) mixing anhydride, ether reagent and amide in proportion, introducing high-purity nitrogen or/and inert gas to prepare spinning solution, and obtaining organic polymer fiber through electrostatic spinning; the acid anhydride is at least one selected from phthalic anhydride, maleic anhydride, pyromellitic dianhydride and trimellitic anhydride; the ether reagent is at least one selected from 2-aminodiphenyl ether, 3,4 '-diaminodiphenyl ether and 4, 4' -diaminodiphenyl ether; the amide is at least one selected from dimethylformamide, dimethylacetamide, formamide, methylacetamide and dihydroxybenzamide; the mass ratio of the acid anhydride to the ether reagent to the amide is 1: (0.5-3.5): (5-30);
(2) soaking organic polymer fibers in a copper salt solution, wherein the copper salt solution is at least one of a copper nitrate ethanol solution, a copper acetate ethanol solution and a copper sulfate ethanol solution; taking out, placing in a trimesic acid solution, then placing in ethanol for soaking, taking out, drying, and repeatedly soaking to obtain HKUST-1 seed crystal/organic polymer fiber;
(3) heating the HKUST-1 seed crystal/organic polymer fiber at 200-400 deg.C at a heating rate of 1-10 deg.C/min; taking out and soaking in a solution containing copper salt and trimesic acid, wherein the solvent is ethanol and water; the mass ratio of the HKUST-1 seed crystal/organic polymer fiber, the copper salt and the trimesic acid is 1: (1-15): (0.5 to 7.5); and sealing, heating for reaction, taking out, and performing suction filtration, washing and drying to obtain the metal organic framework fiber material.
2. The method of claim 1, wherein: in the step (1), the acid anhydride is pyromellitic dianhydride; the ether reagent is 3, 4' -diaminodiphenyl ether; the amide is a dihydroxybenzamide.
3. The method according to claim 1 or 2, characterized in that: in the step (1), the mass ratio of the acid anhydride to the ether reagent to the amide is 1: (0.8-1.5): (8.5-15).
4. The method of claim 1, wherein: in the step (1), the inert gas is at least one of helium and argon, the gas flow rate of the high-purity nitrogen or/and the inert gas is 15 mL/min-35 mL/min, and the ventilation time is 3 h-7 h.
5. The method of claim 1, wherein: and (2) after gas is introduced in the step (1), preparing the spinning solution at the temperature of-10-35 ℃ and the stirring speed of 150-300 rpm.
6. The method of claim 5, wherein: the spinning solution is prepared at the temperature of-3 ℃ to 15 ℃.
7. The method of claim 1, wherein: in the step (1), the organic polymer fiber obtained by electrostatic spinning has the diameter of 450 nm-550 nm and the specific surface area of 35m2/g～65m2Per g, pore volume of 0.1cm3/g～0.3 cm3/g。
8. The method of claim 1, wherein: in the step (2), the copper salt solution is a cupric nitrate ethanol solution.
9. The method according to claim 1 or 8, characterized in that: in the copper salt solution in the step (2), the mass concentration of the copper salt is 0.1-5%.
10. The method of claim 9, wherein: in the copper salt solution in the step (2), the mass concentration of the copper salt is 0.5-2%.
11. The method according to claim 1 or 8, characterized in that: in the step (2), the mass ratio of the organic polymer fiber to the copper salt is 1: (0.1 to 3).
12. The method of claim 11, wherein: in the step (2), the mass ratio of the organic polymer fiber to the copper salt is 1: (0.5 to 1.5).
13. The method of claim 1, wherein: in the step (2), the mass concentration of trimesic acid in the trimesic acid solution is 0.1-5%.
14. The method of claim 13, wherein: in the trimesic acid solution, the mass concentration of the trimesic acid is 0.5-2%.
15. The method according to claim 1 or 13 or 14, characterized in that: in the step (2), the mass ratio of the organic polymer fibers to the trimesic acid is 1: (0.05-1.5).
16. The method of claim 15, wherein: in the step (2), the mass ratio of the organic polymer fibers to the trimesic acid is 1: (0.25-0.75).
17. The method of claim 1, wherein: in the step (2), the material is soaked in ethanol for 1-10 min, then taken out and dried under the protection of inert gas, the drying temperature is 20-30 ℃, and the drying time is 5-10 h; drying and then repeatedly dipping.
18. The method of claim 1, wherein: in the step (3), the HKUST-1 seed crystal/organic polymer fiber is transferred to a muffle furnace for heating treatment, wherein the treatment temperature is 260-330 ℃; the heating rate is 3-6 deg.C/min.
19. The method of claim 1, wherein: in the step (3), the copper salt is selected from one or more of copper nitrate, copper acetate and copper sulfate; in the solution containing copper salt and trimesic acid, the mass concentration of the copper salt is 1-20 percent, and the mass concentration of the trimesic acid is 1-20 percent.
20. The method of claim 19, wherein: in the step (3), in the solution containing copper salt and trimesic acid, the mass concentration of the copper salt is 5-10%; the mass concentration of the trimesic acid is 2.5-5%.
21. The method of claim 1 or 19 or 20, wherein: in the step (3), in the solution containing the copper salt and the trimesic acid, the solvent is ethanol and water, and the mass ratio of the ethanol to the water is 1: (0.5 to 3).
22. The method of claim 1, wherein: in the step (3), the mass ratio of the HKUST-1 seed crystal/organic polymer fiber, the copper salt and the trimesic acid is 1: (5-10): (2.5-5).
23. The method of claim 1, wherein: in the step (3), the heating temperature after sealing is 70-150 ℃, and the heating time is 8-15 h.
24. The method of claim 1, wherein: in the step (3), an ethanol water solution is adopted for washing, and the mass ratio of ethanol to water is 1: (0.5 to 3); the drying temperature is 50-200 ℃, and the drying time is 6-10 h.
25. The method of claim 24, wherein: in the step (3), the drying is carried out under the protection of high-purity nitrogen or/and inert gas, wherein the inert gas is at least one of helium and argon.
26. A metal-organic framework fibrous material, characterized in that it has been prepared by a process according to any one of claims 1 to 25.
27. Use of a metal-organic framework fibrous material according to claim 26, characterized in that: the method is used for selective adsorption separation of ethylene/nitrogen, propylene/nitrogen and ethane/nitrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711279609.7A CN109876775B (en) | 2017-12-06 | 2017-12-06 | Metal organic framework fiber material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711279609.7A CN109876775B (en) | 2017-12-06 | 2017-12-06 | Metal organic framework fiber material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109876775A CN109876775A (en) | 2019-06-14 |
| CN109876775B true CN109876775B (en) | 2022-04-08 |
Family
ID=66924403
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711279609.7A Active CN109876775B (en) | 2017-12-06 | 2017-12-06 | Metal organic framework fiber material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109876775B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110787778A (en) * | 2019-11-01 | 2020-02-14 | 中国工程物理研究院材料研究所 | Modified fiber ball filtering and adsorbing material and preparation method and application thereof |
| CN114481621B (en) * | 2022-01-20 | 2023-04-28 | 南通大学 | Preparation method of multifunctional wool loaded with Cu-MOFs |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2907569B1 (en) * | 2012-10-10 | 2018-08-22 | Nanjing Tech University | Regeneration method for cu-btc material |
| KR101759774B1 (en) * | 2015-04-21 | 2017-07-20 | 부산대학교 산학협력단 | A method for preparing core-shell copper nanoparticlesimmobilized on activated carbonandthe preparation of chalcogenide compoundusing them as a catalyst |
| CN107201645A (en) * | 2017-04-28 | 2017-09-26 | 东华大学 | A kind of metal organic frame/carbon nano-fiber composite film material and preparation method thereof |
-
2017
- 2017-12-06 CN CN201711279609.7A patent/CN109876775B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109876775A (en) | 2019-06-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107159130B (en) | Preparation method of metal-organic framework fiber membrane | |
| CN109956463B (en) | Carbon nano tube and preparation method thereof | |
| CN106299385B (en) | N doping carbonization bacterial cellulose loaded nanometer platinum electrode material and preparation method thereof | |
| CN105780198A (en) | Preparation method of ordered mesoporous carbon nanofibers | |
| CN107099880B (en) | Cobalt nickel oxide/tin dioxide composite nanotube and preparation method and application thereof | |
| CN109433024B (en) | Membrane material or aerogel material containing metal organic framework nanofiber as well as preparation method and application thereof | |
| KR20220067896A (en) | Carbon metal-organic framework composite, manufacturing method thereof, and lithium air battery comprising the same | |
| CN112265981B (en) | Method for preparing carbon nano tube by lignin nano micelle | |
| CN108273564B (en) | Composite visible light photocatalyst Ag2CO3/TiO2/UiO-66-(COOH)2Preparation method and application thereof | |
| CN109876775B (en) | Metal organic framework fiber material and preparation method thereof | |
| CN107376888B (en) | Flexible titanium oxide/silicon oxide/carbon composite nanofiber membrane and preparation method thereof | |
| CN107930591B (en) | Super-gravity method metal organic ligand doped amino acid composite material and preparation method thereof | |
| CN103111274B (en) | Preparation method of graphene/TiO2 fiber | |
| CN101301592A (en) | Preparation of polyimides/titanic oxide compound sub-micron fiber film | |
| CN111821952A (en) | Preparation method of polyvinylidene fluoride/graphene oxide/metal organic framework three-phase composite material | |
| KR20140135306A (en) | Crystalline Iridium Oxide Nanoparticles Decorated on the One Dimensional Metal Oxide Nano-fibers as Water Oxidation Catalyst and Fabrication Method for Preparing the Same | |
| CN106732385A (en) | Composite magnetic hybrid material Fe3O4/ MOFs and its preparation method and application | |
| CN108993452A (en) | A kind of preparation method of the magnetic coupling hydrogel for copper absorption | |
| CN110578254B (en) | PAN/ZIF-67 composite material with adjustable load form and preparation method thereof | |
| CN113976088A (en) | Preparation method of polyamide 6/graphene oxide/iron-based metal organic framework three-phase composite material | |
| CN112705167A (en) | Preparation method of MOF (Metal organic framework) modified activated carbon brick and application of MOF modified activated carbon brick in large-air-volume air filtration | |
| CN109860485A (en) | A kind of polyimide nano-fiber diaphragm and its manufacturing method | |
| CN112999896A (en) | Boehmite modified adsorption film and preparation method and application thereof | |
| Zhang et al. | Controllable synthesis of peapod-like TiO 2@ GO@ C electrospun nanofiber membranes with enhanced mechanical properties and photocatalytic degradation abilities towards methylene blue | |
| CN114242986A (en) | Self-supporting multi-stage structure vanadium nitride-based carbon nanofiber composite material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231025 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |