CN114849651A - Activated carbon packaged carboxylic acid metal organic framework composite material, preparation thereof and gas adsorption separation application - Google Patents
Activated carbon packaged carboxylic acid metal organic framework composite material, preparation thereof and gas adsorption separation application Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 265
- 239000000463 material Substances 0.000 title claims abstract description 58
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims abstract description 46
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 46
- 239000012924 metal-organic framework composite Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000000926 separation method Methods 0.000 title claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 75
- 239000000243 solution Substances 0.000 claims abstract description 52
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 36
- 239000011148 porous material Substances 0.000 claims abstract description 28
- 239000003446 ligand Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000002791 soaking Methods 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 38
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 30
- 229910021645 metal ion Inorganic materials 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 7
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 5
- 239000005750 Copper hydroxide Substances 0.000 claims description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 5
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 4
- 239000003610 charcoal Substances 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 2
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 240000007049 Juglans regia Species 0.000 claims description 2
- 235000009496 Juglans regia Nutrition 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- 235000009827 Prunus armeniaca Nutrition 0.000 claims description 2
- 244000018633 Prunus armeniaca Species 0.000 claims description 2
- -1 amino, hydroxyl Chemical group 0.000 claims description 2
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003830 anthracite Substances 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910001338 liquidmetal Inorganic materials 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 235000020234 walnut Nutrition 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 abstract description 51
- 125000000524 functional group Chemical group 0.000 abstract description 7
- 238000007598 dipping method Methods 0.000 abstract description 3
- 238000004806 packaging method and process Methods 0.000 abstract description 3
- 239000013081 microcrystal Substances 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 35
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 19
- 239000013148 Cu-BTC MOF Substances 0.000 description 18
- 239000010949 copper Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- NOSIKKRVQUQXEJ-UHFFFAOYSA-H tricopper;benzene-1,3,5-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1.[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 NOSIKKRVQUQXEJ-UHFFFAOYSA-H 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000003213 activating effect Effects 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000007810 chemical reaction solvent Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- GPWDPLKISXZVIE-UHFFFAOYSA-N cyclo[18]carbon Chemical compound C1#CC#CC#CC#CC#CC#CC#CC#CC#C1 GPWDPLKISXZVIE-UHFFFAOYSA-N 0.000 description 4
- 239000002149 hierarchical pore Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007783 nanoporous material Substances 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- JYOPEUXKTQSNKH-UHFFFAOYSA-N [N+](=O)([O-])[O-].[Cu+2].[O-2].[Zn+2] Chemical compound [N+](=O)([O-])[O-].[Cu+2].[O-2].[Zn+2] JYOPEUXKTQSNKH-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000003636 chemical group Chemical group 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- HQUYBLKIOPTDRU-UHFFFAOYSA-N copper oxocopper dinitrate Chemical compound [N+](=O)([O-])[O-].[Cu+2].[Cu]=O.[N+](=O)([O-])[O-] HQUYBLKIOPTDRU-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000013152 imidazole-based metal-organic framework Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical group [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 1
- 238000002429 nitrogen sorption measurement Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000034655 secondary growth Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
- B01J20/0237—Compounds of Cu
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- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/10—Single element gases other than halogens
- B01D2257/102—Nitrogen
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2257/702—Hydrocarbons
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- B01D2257/7025—Methane
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Abstract
The invention belongs to the technical field of hierarchical porous composite carbon materials, and particularly relates to an activated carbon packaging carboxylic acid metal organic framework composite material, and preparation and gas adsorption separation application thereof. The composite material is a hierarchical porous composite carbon material with the general formula of AC x ·MOF y Wherein AC ═ activated carbon, MOF ═ metal organic framework material having carboxylic acid ligand adsorbed, x: y is 200-500; the mass ratio of the AC is 80-90 wt%, and the mass ratio of the MOF is 10-20 wt%. The composite material is prepared by alternately dipping the activated carbon in a metal salt solution and a carboxylic acid ligand solution and carrying out a soaking reaction. The compounded carbon material forms porous microcrystal MOF, has smaller pore diameter, can obviously increase the content of micropores and obviously improve the specific surface area,the functional group types of the composite material are increased, so that the selectivity and the adsorption quantity of the composite carbon material are improved.
Description
Technical Field
The invention belongs to the technical field of hierarchical porous composite carbon materials, and particularly relates to an activated carbon packaging carboxylic acid metal organic framework composite material, and preparation and gas adsorption separation application thereof.
Background
The Metal Organic Framework (MOF) is a crystalline porous material formed by self-assembly of Metal ions or ion clusters and multifunctional organic ligands through coordination bonds, has extremely high porosity, large specific surface area and highly controllable pore channel structure, and has rich chemical composition and diversified topological structure. However, it is difficult to practically apply the method to actual industries because of its poor stability and high manufacturing cost. Carbon-based porous materials (such as Activated Carbon (AC)) have developed pore structures, large specific surface areas and abundant surface chemical groups, and are very stable, but selective adsorption is difficult because the materials have no regular and ordered pore channel structures. Considering that the two materials have advantages and disadvantages, the two materials are combined to enhance the advantages and make up for the defects, the composite hierarchical pore carbon material is expected to obtain larger specific surface area, more micropores and enhanced selectivity and stability of the composite hierarchical pore carbon material, and meanwhile, the activated carbon can provide abundant mesopores and macropores and can improve the diffusion capacity.
The Cu-BTC framework, namely copper 1,3, 5-tricarboxylate, also called HKUST-1, is one of the most widely studied gas separation and storage MOFs due to its high specific surface area, large pore volume and good thermal stability. For example for adsorbing CO 2 . Up to now, HKUST-1 has been concerned with CO adsorption 2 The study mainly focused on CO regulation by material design or post-synthesis modification 2 Adsorption capacity/selectivity of. However, MOF adsorption materials have the sensitive drawback of water vapor, resulting in limited applications. Since HKUST-1 is hydrophilic, the water molecules have a strong affinity for the copper centers in the HKUST-1 framework. If it can be encapsulated in hydrophobic activated carbon, it is hopeful to avoid the influence of water vapor on the Cu-BTC skeleton.
In addition, MOF materials are relatively expensive to manufacture and also suffer from high pressure drop due to their powder-type adsorbents, further limiting their practical applications. The activated carbon has a wide application in the aspect of waste gas treatment, and is generally used as columnar activated carbon for waste gas treatment, but the activated carbon has a disordered pore structure and no selective adsorption capacity, and usually only has a simple adsorption function. Meanwhile, the content of the micropores directly determines the specific surface area of the activated carbon and also influences the adsorption capacity of the activated carbon. Therefore, if a small amount of MOF can be introduced into the formed columnar activated carbon, it is expected to increase the content of micropores of the activated carbon, thereby increasing the specific surface area and adsorption capacity thereof, increasing the types of functional groups, and the MOF can be introduced to have the selective adsorption performance without the problems of high powder pressure drop, high cost, and the like.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide an activated carbon encapsulated carboxylic acid metal-organic framework composite material, which enables the MOFs (nano-porous materials) to grow in macropores of activated carbon through the organic combination of the activated carbon and the metal-organic framework material, so that the micropore content is increased, the specific surface area is increased, the types of functional groups of the composite material are increased, and the selectivity and the adsorption capacity of the composite carbon material are improved.
In order to realize the purpose, the invention is realized by the following technical scheme:
the invention provides an active carbon encapsulated carboxylic acid metal organic framework composite material (MOF @ AC material for short), and the general formula of the composite material is AC x ·MOF y Wherein AC ═ activated carbon, MOF ═ metal organic framework material having carboxylic acid ligand adsorbed, x: y is 200-500; the mass ratio of the AC is 80-90 wt%, the mass ratio of the MOF is 10-20 wt%, the AC comprises at least one of coconut shell carbon, apricot shell carbon, walnut shell carbon, anthracite activated carbon, bamboo charcoal and charcoal, the AC is formed activated carbon, and the shape of the AC comprises granular, columnar and spherical shapes.
The invention also provides a preparation method of the activated carbon encapsulated carboxylic acid metal organic framework composite material, which comprises the steps of adsorbing metal ions or molten metal salt on the surface of the activated carbon and in the inner pore channel, then reacting in a carboxylic acid ligand solution to generate the activated carbon encapsulated imidazole metal organic framework composite material, and finally removing solvent molecules in the pore channel of the composite material through activation.
Preferably, the metal organic framework material includes, but is not limited to, Cu-BTC (C) 18 H 12 Cu 3 O 15 ). In a preferred embodiment of the present invention, the metal organic framework material is selected from Cu-BTC.
The Cu-BTC @ AC composite carbon material prepared by Cu-BTC can promote the formation of the Cu-BTC @ AC composite material through oxygen-containing functional groups on the surface of the activated carbon and pi-pi interaction between the Cu-BTC and an aromatic ring of the activated carbon. The specific surface area of the compounded carbon material can be obviously increased, so that the adsorption capacity of gas is increased, mainly because the ligand and copper ions form porous microcrystal Cu-BTC in the preparation process, the specific surface area is higher, and the pore diameter is smaller.
In a preferred embodiment of the present invention, the method for preparing the activated carbon encapsulated carboxylic acid-based metal organic framework composite material comprises the following steps:
s1, soaking the activated carbon in a metal ion solution or liquid molten metal salt, adsorbing the metal ions or the molten metal salt in the surface and the inner pore channels of the activated carbon, and preparing the activated carbon rich in the metal ions or the liquid metal molten salt in the surface and the inner pore channels;
s2, soaking the activated carbon obtained in the step S1 in a carboxylic acid ligand solution, and preparing the activated carbon-encapsulated imidazole metal-organic framework composite material after full reaction;
s3, drying the activated carbon packaged imidazole metal organic framework composite material obtained in the step S2, and then placing the dried material at 80-200 ℃ for vacuum activation for 8-16 h to remove solvent molecules in the pore channel, so as to obtain the final activated carbon packaged imidazole metal organic framework composite material.
In another preferred embodiment of the present invention, after step S1 is completed, the metal ions adsorbed on the activated carbon are converted into metal oxides, and then the carboxylic acid ligand reaction in step S2 is performed to prepare the activated carbon encapsulated imidazole based metal organic framework composite material.
Further, the method for converting the metal ions adsorbed in the activated carbon into metal oxides is as follows: and putting the activated carbon adsorbed with the metal ions into an ethanolamine aqueous solution for reacting for 24-36h in a greenhouse.
MOFs materials have good application prospects, such as gas storage, molecular separation in gas and liquid mixtures, catalysis, chiral separation, sensors for special types of molecules, and the like, due to various topological structures and excellent performance. However, due to poor stability, high cost and difficult molding, no mature technology is applied in the actual industry at present. In contrast, the application technology of activated carbon is well established. The activated carbon also has a developed pore structure, a large specific surface area and abundant surface chemical groups, but has no regularly ordered pores and poor selectivity. The MOFs is a microporous material, and the activated carbon has micropores, mesopores and macropores at the same time, so that the two materials are organically combined, the nano porous material MOFs grows in the macropores of the activated carbon, the micropore content can be increased, the specific surface area can be increased, the types of functional groups of the composite material can be increased, and the selectivity and the adsorption capacity of the composite carbon material can be improved.
Further, after the imidazole-based metal organic framework composite material encapsulated by the activated carbon is prepared in the step S2, the composite material is repeated for a plurality of times through the operations of the steps S1 and S2, and the loading capacity of the carboxylic acid ligand and the metal organic framework material is improved through secondary growth.
The invention prepares the hierarchical porous composite carbon material by using a 'shipbuilding in bottles' method in Activated Carbon (AC), namely the hierarchical porous composite carbon material is prepared by alternately dipping the activated carbon in a metal salt solution and a ligand solution and repeatedly soaking, and the specific surface area of the MOF @ AC material can be obviously increased.
Further, the number of cycles for repeating the operations of the steps S1 and S2 a plurality of times is 3-20 times.
Further, the carboxylic acid ligand comprises terephthalic acid and trimesic acid, hydrogen at the ortho position of the terephthalic acid can be replaced by R, and R comprises amino, hydroxyl, methyl and nitro. Specifically, the carboxylic acid ligand is trimesic acid.
Further, the source of the metal ions in the metal ion solution comprises copper nitrate trihydrate, copper hydroxide, and a mixture of copper nitrate trihydrate and copper oxide; the molten metal salt comprises molten copper nitrate trihydrate. Other divalent or trivalent metal ions (e.g. Fe) 3+ 、Cr 3+ ) The same applies to the present invention.
Further, the molten metal salt is obtained directly by melting by heating.
Furthermore, the reaction temperature in the carboxylic acid ligand solution is 20-100 ℃, and the reaction time is 3-24 h.
Further, in the metal salt solution, the concentration of metal ions is 100-400 g/L; the concentration of the carboxylic acid ligand solution is 100-400 g/L.
Further, the solvent for preparing the metal ion solution and the carboxylic acid ligand solution comprises ethanol, water and N, N-dimethylformamide.
Specifically, the active carbon is columnar active carbon WS-480 with the diameter of about 3-4 mm, is microporous carbon, and has the BET specific surface area of 1137m 2 /g。
The invention provides application of the activated carbon encapsulated carboxylic acid metal organic framework composite material in gas adsorption separation, wherein the gas adsorption separation comprises CO adsorption 2 Adsorbing N 2 Adsorption of C 2 H 6 。
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses an activated carbon packaging carboxylic acid metal organic framework composite material which is a hierarchical pore composite carbon material with a general formula of AC x ·MOF y Wherein AC ═ activated carbon, MOF ═ metal organic framework material having carboxylic acid ligand adsorbed, x: y is 200-500; the mass ratio of the AC is 80-90 wt%, and the mass ratio of the MOF is 10-20 wt%. Meanwhile, the invention also discloses a simple and efficient method for preparing the composite material, namely the composite material is prepared by alternately dipping the activated carbon in a metal salt solution and a carboxylic acid ligand solution, and growing the nano porous material MOFs in macropores of the activated carbon through a soaking reactionAnd obtaining the hierarchical pore composite carbon material. The composite carbon material can promote the formation of the MOF @ AC composite material through oxygen-containing functional groups on the surface of the activated carbon and pi-pi interaction between the MOF and an activated carbon aromatic ring, the composite carbon material forms porous microcrystalline MOF, the pore size is smaller, the micropore content can be obviously increased, the specific surface area is obviously improved, the functional group type of the composite material is increased, and therefore the selectivity and the adsorption capacity of the composite carbon material are improved.
Drawings
FIG. 1 is an XRD pattern of Cu-BTC @ AC prepared in example 1;
FIG. 2 is a FT-IR spectrum of Cu-BTC @ AC prepared in example 1;
FIG. 3 is a thermogravimetric analysis plot of Cu-BTC @ AC prepared in example 1;
FIG. 4 is an SEM image of (a) activated carbon, (b) Cu-BTC and (c, d) Cu-BTC @ AC;
FIG. 5 is a nitrogen sorption and desorption test curve for Cu-BTC @ AC prepared in example 1;
FIG. 6 is a mercury intrusion adsorption curve for Cu-BTC @ AC prepared in example 1;
FIG. 7 is a representation of Cu-BTC @ AC vs. C prepared in example 1 2 H 6 The adsorption curve of (c);
FIG. 8 is a graphical representation of Cu-BTC @ AC prepared in example 1 vs. CO at 298K 2 The adsorption curve of (c);
FIG. 9 Cu-BTC @ AC prepared in example 1 vs. CO at 273K 2 Adsorption curve of (2).
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The experimental procedures in the following examples were carried out by conventional methods unless otherwise specified, and the test materials used in the following examples were commercially available by conventional methods unless otherwise specified.
Example 1 active carbon-encapsulated carboxylic acid metal organic framework composite material (Cu-BTC @ AC composite carbon material) and preparation method thereof
The structural formula of the Cu-BTC @ AC composite carbon material is as follows: AC 220 ·(C 18 H 12 Cu 3 O 15 ) 1 AC ═ 85 wt% of activated carbon, C ═ 85 wt% of carbon 18 H 12 Cu 3 O 15 15 wt%. The preparation method of the Cu-BTC @ AC composite carbon material comprises the following steps:
(1) preparation of reaction solvent
Adding 0.293g of CuO into 8mL of deionized water, adding 16mL of DMF, and performing ultrasonic dispersion for 10min to prepare a copper oxide dispersion liquid; then 1.74g of Cu (NO) 3 ) 2 3(H 2 O) is dissolved in 8mL of deionized water to prepare a copper nitrate solution; then adding the copper nitrate solution into the copper oxide dispersion liquid to prepare a copper nitrate-copper oxide solution; 0.84g of trimesic acid was added to 16mL of anhydrous ethanol and stirred until dissolved to prepare an ethanol solution of trimesic acid.
(2) Preparation of Cu-BTC @ AC composite carbon material
Firstly, columnar active carbon WS-480 (the diameter is about 3-4 mm, and the BET specific surface area reaches 1137 m) 2 And/g) placing the carbon powder in a copper nitrate-copper oxide solution for soaking for 30min, performing ultrasonic treatment for 20min, taking out the activated carbon adsorbed with the metal ion solution, and placing the activated carbon in an oven at 80 ℃ for drying for 24h to volatilize the solvent. Then putting the mixture into an ethanol solution of trimesic acid under the condition of stirring to react for 4 hours at room temperature, taking out the mixture and putting the mixture into an oven to dry until the solvent is completely volatilized. The above operation is repeated for a plurality of times, and the activated carbon is circularly reacted for 6 times in the two solutions. And after the reaction is finished, preparing the Cu-BTC @ AC composite carbon material, and sequentially soaking the prepared composite carbon material in DMF (dimethyl formamide) and absolute ethyl alcohol solution for 3 times, wherein each time lasts for 30 min. Finally, drying in an oven at 80 ℃ for 24h, and vacuum activating at 150 ℃ for 10h to remove the guest molecules (solvent) in the pore channels.
Example 2 activated carbon-encapsulated carboxylic acid metal organic framework composite material (Cu-BTC @ AC composite carbon material) and preparation method thereof
The structural formula of the Cu-BTC @ AC composite carbon material is as follows: AC (alternating current) 494 ·(C 18 H 12 Cu 3 O 15 ) 1 AC ═ 90 wt% of activated carbon, C ═ 90 wt% of carbon 18 H 12 Cu 3 O 15 10 wt%. The preparation method of the Cu-BTC @ AC composite carbon material comprises the following steps:
(1) preparation of reaction solvent
Adding 0.4g of trimesic acid into 6mL of absolute ethyl alcohol, 6mL of DMF and 6mL of deionized water, and stirring until the mixture is dissolved; 2.5g of Cu (NO) 3 ) 2 3(H 2 O) heating to a molten state.
(2) Preparation of Cu-BTC @ AC composite carbon material
Firstly, columnar active carbon WS-480 (the diameter is about 3-4 mm, and the BET specific surface area reaches 1137 m) 2 /g) in molten copper nitrate trihydrate, ultrasonically soaking for 30min, and then airing the activated carbon adsorbed with the molten copper nitrate at room temperature. The solution is put into the trimesic acid solution while stirring for 15min at room temperature, and then the solution containing the activated carbon is transferred into a reaction kettle and reacted for 10h at 100 ℃. And after the reaction is finished, taking out the obtained product and putting the product into an oven to dry until the solvent is completely volatilized, preparing the Cu-BTC @ AC composite carbon material, and sequentially putting the prepared composite carbon material into DMF (dimethyl formamide) and absolute ethyl alcohol solution to soak for 3 times, wherein each time is 30 min. Finally, drying in an oven at 80 ℃ for 24h, and vacuum activating at 150 ℃ for 10h to remove the guest molecules (solvent) in the pore channels.
Example 3 carboxylic acid metal organic framework composite material (Cu-BTC @ AC composite carbon material) encapsulated by activated carbon and preparation method thereof
The structural formula of the Cu-BTC @ AC composite carbon material is as follows: AC (alternating current) 494 ·(C 18 H 12 Cu 3 O 15 ) 1 AC ═ 90 wt% of activated carbon, C ═ 90 wt% of carbon 18 H 12 Cu 3 O 15 10 wt%. The preparation method of the Cu-BTC @ AC composite carbon material comprises the following steps:
(1) preparation of reaction solvent
0.831g of Cu (NO) 3 ) 2 3(H 2 O) is dissolved in 6mL of deionized water to prepare a copper nitrate solution; 0.4g of trimesic acid was dissolved in 6mL of absolute ethanol and 6mL of DMF, and the mixture was stirred at room temperature until it was dissolvedDecomposing to prepare trimesic acid solution.
(2) Preparation of Cu-BTC @ AC composite carbon material
Firstly, columnar active carbon WS-480 (the diameter is about 3-4 mm, and the BET specific surface area reaches 1137 m) 2 And/g) placing the mixture in a copper nitrate solution for soaking for 30min, performing ultrasonic treatment for 20min, taking out the activated carbon adsorbed with the metal ion solution, placing the activated carbon in an oven at 80 ℃ for drying for 24h, and volatilizing the solvent. And putting the mixture into a reaction kettle filled with a trimesic acid solution under the condition of stirring, reacting for 24 hours at the temperature of 100 ℃, taking out the mixture, putting the mixture into an oven, and drying until the solvent is completely volatilized. The above operation was repeated a plurality of times to circulate the activated carbon in both solutions for 6 times. And after the reaction is finished, preparing the Cu-BTC @ AC composite carbon material, and sequentially soaking the prepared composite carbon material in DMF (dimethyl formamide) and absolute ethyl alcohol solution for 3 times, wherein each time lasts for 30 min. Finally, drying in an oven at 80 ℃ for 24h, and vacuum activating at 150 ℃ for 10h to remove the guest molecules (solvent) in the pore channels.
Example 4 active carbon-encapsulated carboxylic acid metal organic framework composite material (Cu-BTC @ AC composite carbon material) and preparation method thereof
The structural formula of the Cu-BTC @ AC composite carbon material is as follows: AC 311 ·(C 18 H 12 Cu 3 O 15 ) 1 AC 85 wt% of activated carbon, C 18 H 12 Cu 3 O 15 15 wt%. The preparation method of the Cu-BTC @ AC composite carbon material comprises the following steps:
(1) preparation of reaction solvent
Adding 1.96g of copper hydroxide into 10mL of deionized water, and ultrasonically dispersing in an ice-water bath for 10min to prepare copper hydroxide slurry; 4.2g of trimesic acid was added to 10mL of ethanol and stirred until dissolved to prepare an ethanol solution of trimesic acid.
(2) Preparation of Cu-BTC @ AC composite carbon material
Firstly, columnar active carbon WS-480 (the diameter is about 3-4 mm, and the BET specific surface area reaches 1137 m) 2 And/g) placing the mixture in copper hydroxide slurry for soaking for 30min, performing ultrasonic treatment for 20min, taking out the activated carbon, placing the activated carbon in an oven at 100 ℃ for drying for 24h, and volatilizing the solvent. With stirring and with additional trimesic acidReacting in an ethanol solution at room temperature for 3 hours, taking out, and drying in an oven until the solvent is completely volatilized. The above operation was repeated a plurality of times to circulate the activated carbon in both solutions for 6 times. And after the reaction is finished, preparing the Cu-BTC @ AC composite carbon material, and sequentially soaking the prepared composite carbon material in DMF (dimethyl formamide) and absolute ethyl alcohol solution for 3 times, wherein each time lasts for 30 min. Finally, drying in an oven at 80 ℃ for 24h, and vacuum activating at 150 ℃ for 10h to remove the guest molecules (solvent) in the pore channels.
Example 5 active carbon-encapsulated carboxylic acid metal organic framework composite material (Cu-BTC @ AC composite carbon material) and preparation method thereof
The structural formula of the Cu-BTC @ AC composite carbon material is as follows: AC 311 ·(C 18 H 12 Cu 3 O 15 ) 1 AC ═ 85 wt% of activated carbon, C ═ 85 wt% of carbon 18 H 12 Cu 3 O 15 15 wt%. The preparation method of the Cu-BTC @ AC composite carbon material comprises the following steps:
(1) preparation of reaction solvent
20mmol of Cu (NO) 3 ) 2 3(H 2 O) is added into 20mL of deionized water, and the mixture is stirred at room temperature until the mixture is dissolved to prepare copper nitrate aqueous solution; adding 2mL of ethanolamine into 10mL of deionized water, and uniformly mixing to prepare an ethanolamine aqueous solution; dissolving 3g of trimesic acid in 6mL of deionized water and 6mL of absolute ethyl alcohol, and stirring at room temperature until the solution is dissolved to prepare a trimesic acid solution.
(2) Preparation of CuO @ AC
Firstly, columnar active carbon WS-480 (the diameter is about 3-4 mm, and the BET specific surface area reaches 1137 m) 2 And/g) placing the mixture in a copper nitrate aqueous solution for soaking for 30min, performing ultrasonic treatment for 20min, taking out the activated carbon adsorbed with the metal ion solution, placing the activated carbon in an oven at 80 ℃ for drying for 24h, and volatilizing the solvent. And putting the mixture into an ethanolamine aqueous solution under the condition of stirring, and reacting for 24 hours at the constant temperature of 25 ℃ to obtain CuO @ AC. The above operation was repeated a plurality of times to circulate the activated carbon in both solutions for 6 times. And after the reaction is finished, preparing CuO @ AC, sequentially placing the prepared CuO @ AC into deionized water and absolute ethyl alcohol, soaking for 3 times, each time for 30min, and finally drying in an oven at 80 ℃ for 24 h.
(3) Preparation of Cu-BTC @ AC composite carbon material
And (3) adding the CuO @ AC into an ethanol water solution of trimesic acid for reaction at room temperature for 12 hours, taking out the CuO @ AC, and putting the CuO @ AC into an oven for drying until the solvent is volatilized. And after the reaction is finished, preparing the Cu-BTC @ AC composite carbon material, and sequentially soaking the prepared composite carbon material in deionized water and absolute ethyl alcohol for 3 times, wherein each time lasts for 30 min. Finally, drying in an oven at 80 ℃ for 24h, and activating in vacuum at 150 ℃ for 10h to remove the guest molecules in the pore channels.
Comparative example 1 pure Cu-BTC powder preparation procedure
Adding 0.293g of ZnO into 8mL of deionized water, adding 16mL of DMF, and performing ultrasonic dispersion for 10min to prepare zinc oxide dispersion; then 1.74g of Cu (NO) 3 ) 23 (H 2 O) is dissolved in 8mL of deionized water to prepare a copper nitrate solution; and adding the copper nitrate solution to the zinc oxide dispersion to prepare a copper nitrate-zinc oxide solution. Then, 0.84g of trimesic acid was added to 16mL of anhydrous ethanol and stirred until dissolved to prepare an ethanol solution of trimesic acid. And finally, adding the ethanol solution of the trimesic acid into the copper nitrate-zinc oxide solution. Covering with a preservative film after the reaction is finished, continuously reacting for 10min at room temperature under the condition of stirring, centrifuging the product for 5min at the rotating speed of 8000r/min, washing for 3 times by using methanol, and finally drying in an oven at 70 ℃ for 8 hours or in a vacuum oven at 70 ℃ for 4 hours.
Experimental example 1 characterization and Performance testing of Cu-BTC @ AC composite carbon Material
Taking the Cu-BTC @ AC composite carbon material of example 1 as an example, and taking pure Cu-BTC and activated carbon AC as a control, the following characteristics and performance tests are carried out:
(1) characterization by X-ray diffraction analysis (XRD)
Scanning a sample between 2 theta and 4-40 by using an X-ray diffractometer, wherein the test result is shown in figure 1, and the peak of Cu-BTC which is originally absent in the activated carbon is reflected in the prepared composite material at present, which shows that the Cu-BTC @ AC composite material is successfully prepared.
(2) Fourier transform Infrared Spectroscopy (FT-IR) characterization
In the FT-IR infrared test shown in FIG. 2, the compounded sample has more active carbon peaks than the original sample, and the peaks correspond to the peaks of Cu-BTC, which further illustrates that the Cu-BTC @ AC composite material is successfully prepared.
(3) Thermogravimetric analysis
The thermogravimetric result of fig. 3 shows that, originally, Cu-BTC has a large weight loss at about 300 ℃, and at this time, the framework collapses, but the composite material prepared in this embodiment shows a large weight loss at 340 ℃, and the weight loss curve moves to the right obviously, so the thermal stability is improved to some extent.
(4) Scanning Electron Microscope (SEM) characterization
And breaking the Cu-BTC @ AC particles, and observing by using SEM (scanning Electron microscope), wherein the activated carbon is fully grown with Cu-BTC according to an SEM image shown in figure 4, and further, the Cu-BTC @ AC composite material is successfully prepared.
(5) Nitrogen adsorption and desorption performance test
The nitrogen adsorption test was performed at 77K by a Micromeritics ASAP 2460 adsorber. As can be seen from the nitrogen adsorption curve of FIG. 5, the Cu-BTC @ AC composite material improves the N content of the activated carbon 2 Adsorption capacity, wherein the adsorption capacity of AC is 1137m 2 G, Cu-BTC adsorption amount 1650m 2 The adsorption capacity of Cu-BTC @ AC is 1122m 2 /g。
(6) Mercury intrusion adsorption curve
Mercury intrusion adsorption testing was performed by a MicroActive AutoPore V96001.03 test instrument. The mercury intrusion adsorption results of fig. 6 show that the Cu-BTC @ AC composite material has a reduced pore volume compared to the original activated carbon, indicating an increased micropore content, which is corroborated with the nitrogen adsorption data.
(7)C 2 H 6 Adsorption Performance test
C by Micromeritics ASAP 2460 test Instrument 2 H 6 And (5) performing adsorption test. C of FIG. 7 2 H 6 The adsorption curve shows that the prepared Cu-BTC @ AC composite material can be used for C 2 H 6 And (4) adsorbing.
(8)CO 2 Adsorption Performance test of
CO was performed at 298K and 273K using a Micromeritics ASAP 2460 instrument 2 Testing the adsorption performance of (1). CO of FIGS. 8 and 9 2 The adsorption curve of (A) shows that the Cu-BTC @ AC composite material can be used for CO 2 And (4) adsorbing.
In addition, the characteristics and performance test results of the Cu-BTC @ AC composite carbon materials of examples 2-5 are the same as or similar to those of example 1.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.
Claims (10)
1. The carboxylic acid metal organic framework composite material packaged by activated carbon is characterized in that the general formula of the composite material is AC x ·MOF y Wherein AC ═ activated carbon, MOF ═ metal organic framework material having carboxylic acid ligand adsorbed, x: y is 200-500; the mass ratio of the AC is 80-90 wt%, the mass ratio of the MOF is 10-20 wt%, the AC comprises at least one of coconut shell carbon, apricot shell carbon, walnut shell carbon, anthracite activated carbon, bamboo charcoal and charcoal, the AC is formed activated carbon, and the shape of the AC comprises granular, columnar and spherical shapes.
2. The method for preparing the activated carbon encapsulated carboxylic acid type metal organic framework composite material as claimed in claim 1, is characterized in that metal ions or molten metal salts are adsorbed on the surface of the activated carbon and in the inner pore channel, then the activated carbon encapsulated imidazole type metal organic framework composite material is generated by the reaction in the carboxylic acid type ligand solution, and finally the solvent molecules in the pore channel of the composite material are removed by activation, thus obtaining the activated carbon encapsulated carboxylic acid type metal organic framework composite material.
3. The preparation method of the activated carbon encapsulated carboxylic acid type metal organic framework composite material according to claim 2, characterized by comprising the following steps:
s1, soaking the activated carbon in a metal ion solution or liquid molten metal salt, adsorbing the metal ions or the molten metal salt in the surface and the inner pore channels of the activated carbon, and preparing the activated carbon rich in the metal ions or the liquid metal molten salt in the surface and the inner pore channels;
s2, soaking the activated carbon obtained in the step S1 in a carboxylic acid ligand solution, and preparing the activated carbon-encapsulated imidazole metal-organic framework composite material after full reaction;
s3, drying the activated carbon packaged imidazole metal organic framework composite material obtained in the step S2, and then placing the dried material at 80-200 ℃ for vacuum activation for 8-16 h to remove solvent molecules in the pore channel, so as to obtain the final activated carbon packaged imidazole metal organic framework composite material.
4. The method for preparing the activated carbon encapsulated carboxylic acid type metal organic framework composite material according to the claim 3, wherein after the step S1 is completed, the metal ions absorbed in the activated carbon are converted into metal oxides, and then the carboxylic acid type ligand reaction of the step S2 is performed to prepare the activated carbon encapsulated imidazole type metal organic framework composite material.
5. The method for preparing the activated carbon encapsulated carboxylic acid type metal organic framework composite material according to the claim 3, wherein the step S2 is performed to prepare the activated carbon encapsulated imidazole type metal organic framework composite material, and then the operations of the steps S1 and S2 are repeated for a plurality of times to improve the loading capacity of the carboxylic acid type ligand and the metal organic framework material.
6. The method for preparing the activated carbon encapsulated carboxylic metal organic framework composite material according to claim 3, wherein the carboxylic ligand comprises terephthalic acid and trimesic acid, hydrogen at ortho position of the terephthalic acid can be converted into R, and R comprises amino, hydroxyl, methyl and nitro.
7. The method for preparing the activated carbon encapsulated carboxylic acid type metal organic framework composite material as claimed in claim 3, wherein the source of the metal ions in the metal ion solution comprises copper nitrate trihydrate, copper hydroxide, and a mixture of copper nitrate trihydrate and copper oxide; the molten metal salt includes molten copper nitrate trihydrate.
8. The method for preparing the activated carbon encapsulated carboxylic acid type metal organic framework composite material as claimed in claim 3, wherein the reaction temperature in the carboxylic acid type ligand solution is 20-100 ℃ and the reaction time is 3-24 h.
9. The method for preparing the activated carbon encapsulated carboxylic acid type metal-organic framework composite material as claimed in claim 3, wherein the concentration of metal ions in the metal salt solution is 100-400 g/L; the concentration of the carboxylic acid ligand solution is 100-400 g/L.
10. The use of the activated carbon encapsulated carboxylic acid metal organic framework composite material as claimed in claim 1, wherein the gas adsorption separation comprises adsorption of CO 2 Adsorbing N 2 Adsorption of C 2 H 6 。
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