CN108558918A - A kind of 3-dimensional metal-organic framework material and its preparation method and application - Google Patents
A kind of 3-dimensional metal-organic framework material and its preparation method and application Download PDFInfo
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- CN108558918A CN108558918A CN201810488414.1A CN201810488414A CN108558918A CN 108558918 A CN108558918 A CN 108558918A CN 201810488414 A CN201810488414 A CN 201810488414A CN 108558918 A CN108558918 A CN 108558918A
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- dimensional metal
- framework material
- organic framework
- steel autoclave
- stainless steel
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- 239000000463 material Substances 0.000 title claims abstract description 32
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 49
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 24
- 239000010935 stainless steel Substances 0.000 claims abstract description 24
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011630 iodine Substances 0.000 claims abstract description 22
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 22
- 239000000975 dye Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 10
- 150000007513 acids Chemical class 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000001179 sorption measurement Methods 0.000 claims description 17
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 14
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 9
- 238000004440 column chromatography Methods 0.000 claims description 6
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 claims description 6
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical compound C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 4
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical class CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000003775 Density Functional Theory Methods 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000001045 blue dye Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- XMBWDFGMSWQBCA-RNFDNDRNSA-M iodine-131(1-) Chemical compound [131I-] XMBWDFGMSWQBCA-RNFDNDRNSA-M 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000013384 organic framework Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- HGUZQMQXAHVIQC-UHFFFAOYSA-N n-methylethenamine Chemical compound CNC=C HGUZQMQXAHVIQC-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000000451 tissue damage Effects 0.000 description 1
- 231100000827 tissue damage Toxicity 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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Abstract
The invention discloses a kind of 3-dimensional metal organic framework materials and its preparation method and application, belong to field of material technology.The preparation method of the material includes the following steps：S1, by 3,3 ', 5,5 ' azo benzene tertacarbonic acids, Cd (NO3)2·4H2O, N, N dimethylacetamide solution and methanol solution are mixed to get mixture；S2, mixture is sealed in the stainless steel autoclave of tetrafluoroethene liner, continuous heating 96 hours in 100 DEG C of stainless steel autoclave；S3, stainless steel autoclave are cooled down with 5 DEG C per hour, to be cooled to after room temperature, with N, N dimethylacetylamides wash and isolate yellow crystals repeatedly, and be dried at room temperature for yellow crystals, 3-dimensional metal organic framework material is obtained, chemical formula is [Cd (ABTC) (H2O)2(DMA)]·4DMA.Crystal prepared by the present invention can effectively adsorb iodine and dyestuff.
Description
Technical field
The present invention relates to field of material technology, and in particular to a kind of 3-dimensional metal-organic framework material and preparation method thereof
And application.
Background technology
With the rapid development of modern society and being constantly progressive for science and technology, the burst size of hazardous chemical is continuous
Increase, for example, nuke rubbish, toxic heavy metal ion, organic dyestuff point, this brings weight to the healthy and safe of human and animal
It is big to threaten.Although we are increasing efficient and non-carbon-emitting nuclear energy demand rapidly, the waste of uranium fission generation
The method of dealing carefully with is that there is an urgent need to the safety problems of concern for nuclear power production one of behind.Especially radioiodine (contains129I
And/or131I) as the chief component of nuclear waste, considerable concern has been caused, mainly since it can be via
Respiratory system causes serious tissue damage and canceration to health.In addition,129I and131The radioactive half-life of I point
It Wei not be 8 days and 1.57 × 107Year, body metabolism system can be slowly penetrated.Therefore, design stability and efficient radioiodine is caught
It obtains and has become urgent problem to be solved with storage material.Thus, synthesizing efficient, porous material at low cost, stablizing are used for gas
Mutually and the capture of the iodine of liquid phase is vital.In numerous porous materials, metal-organic framework (Metal-Organic
Frameworks, MOFs) achievement in research it is very abundant, be primarily due to that its specific surface area is high, pore structure is adjustable, pass rule
Then, unique structure and powerful.In addition, organic ligand and metal ion of the selection with different geometric configurations and function
Or cluster coordination, the high porosity not adjustable MOFs of pore structure can be obtained, these design features advantageously form preferably
Surface binding site is conducive to the capture of iodine.
Secondly, organic dyestuff is widely used in the industrial circles such as papermaking, printing, plastics, textile, medicine, but its toxicity
Even carcinogenicity constitutes water environment and human health very important grave danger.Simultaneously as dyestuff is to light and oxidation
Agent is with good stability, and most of dyestuffs is caused to be difficult to degrade.Therefore, there is an urgent need to a kind of low cost and the dyes of environmental protection
Expect adsorption and separation material.
Invention content
The purpose of the invention is to overcome the problems of the prior art, provide 3-dimensional metal-organic framework material and its
Preparation method and application.
A kind of 3-dimensional metal-organic framework material of the present invention, chemical molecular formula are： [Cd(ABTC)(H2O)2
(DMA)] 4DMA, wherein ABTC are indicated：3,3 ', 5,5 '-azo benzene tertacarbonic acids, DMA table show：N,N-dimethylacetamide belongs to
In monoclinic system, space group P21/ c, cell parameter are α (°)=90, β (°)=98.6970
(11), γ (°)=90, volume
The present invention also provides a kind of preparation methods of 3-dimensional metal-organic framework material, include the following steps：
S1, by the 3 of 0.01-0.015g, 3 ', 5,5 '-azo benzene tertacarbonic acids, the Cd (NO of 0.20-0.25g3)2·4H2O、
The n,N-dimethylacetamide solution of 4-5mL and the methanol solution of 4-5mL, which are uniformly mixed, obtains mixture；
S2, mixture is sealed in the stainless steel autoclave of tetrafluoroethene liner, then places stainless steel autoclave
In an oven, stainless steel autoclave is warming up to 100-110 DEG C from room temperature with 10-15 DEG C per hour, and mixture is in 100-110
DEG C stainless steel autoclave in continuous heating 96-100 hours；
After the completion of S3, heating, stainless steel autoclave is cooled down with 5-8 DEG C per hour, waits for that stainless steel autoclave is cooled to
After room temperature, is washed repeatedly with n,N-dimethylacetamide and isolate yellow crystals, and yellow crystals are dried at room temperature for, obtained
To the 3-dimensional metal-organic framework material.
Preferably, the mixture in step S1 is by 3,3 ', 5, the 5 '-azo benzene tertacarbonic acids of 0.01g, the Cd of 0.20g
(NO3)2·4H2O, the n,N-dimethylacetamide solution of 4mL and the methanol solution of 4mL are mixed to get.
Preferably, stainless steel autoclave is heated up since room temperature with 10 DEG C per hour in step S2.
Preferably, stainless steel autoclave is cooled down with 5 DEG C per hour in step S3.
In terms of above-mentioned 3-dimensional metal-organic framework material is applied to waste liquid or exhaust-gas treatment containing elemental iodine.
Above-mentioned 3-dimensional metal-organic framework material is applied to 3-dimensional metal-organic framework material and is applied to Dye Adsorption
Aspect.
Preferably, dyestuff is methylene blue.
Above-mentioned 3-dimensional metal-organic framework material is applied to column chromatography dye separation methylene blue and Congo red.
Compared with prior art, the beneficial effects of the invention are as follows：The present invention rationally designs under the conditions of solvent thermal reaction
And a dimensional microporous crystal is synthesized.Due to the microcellular structure of the crystal, the neutral iodine point under liquid phase and gas phase can be captured
Son, and adsorption capacity is notable, and the saturated extent of adsorption under liquid phase is 680 mgg-1.Using a series of qualitative and quantitative analyses
Method analyzes the adsorption dynamics adsorption kinetics in iodine adsorption process.The crystal that the present invention is prepared cannot be only used for Asia
The selective absorption of methyl blue, it can also be used to column chromatography dye separation methylene blue and Congo red.Therefore, which is one
Effective adsorbent can effectively adsorb iodine and dyestuff.
Description of the drawings
Fig. 1 is H of the present invention4The structural schematic diagram of ABTC；
Fig. 2 (a) is crystal coordination structure schematic diagram of the present invention.
Fig. 2 (b) is the three-dimensional open-framework of b axis directions of the present invention；
Fig. 2 (c) and Fig. 2 (d) is the mallet figure and polyhedron schematic diagram that (4,4) of the invention connect topological structure；
Fig. 2 (e) is the tile structure schematic diagram that (4,4) of the invention connect topological structure.
Fig. 3 is the PXRD spectrograms that crystal of the present invention is simulated and synthesized；
Fig. 4 (a) is the nitrogen adsorption and desorption isothermal curve for the crystal that the present invention is measured at 77K, 1atm；
The pore-size distribution schematic diagram for the crystal that Fig. 4 (b) is calculated for the present invention using density functional theory；
Fig. 5 (a) is that crystal of the present invention adsorbs iodine in n-hexane and discharges the process of iodine in ethanol；
Fig. 5 (b) is crystal of the present invention in absorption iodine and the color change process of release iodine；
Fig. 5 (c) is 20mg crystal of the present invention in 0.4mgmL-1Ultra-violet absorption spectrum in the hexane solution of iodine；
Fig. 6 (a) is the ultra-violet absorption spectrum that crystal of the present invention adsorbs methylene blue dye in DMA solution；
Fig. 6 (b) is the photo of color change after crystal of the present invention adsorbs methylene blue dye for a period of time；
Fig. 7 is the photo record that crystal of the present invention fills into column chromatography separation methylene blue and congo red.
Specific implementation mode
1-7 below in conjunction with the accompanying drawings is described in detail the specific implementation mode of the present invention, it is to be understood that of the invention
Protection domain be not restricted by specific implementation.Based on the embodiments of the present invention, those of ordinary skill in the art exist
The every other embodiment obtained under the premise of not making creative work, shall fall within the protection scope of the present invention.
Embodiment 1
S1, by the 3 of 0.01g, 3 ', 5,5 '-azo benzene tertacarbonic acids, the Cd (NO of 0.2g3)2·4H2O, the N of 4ml, N- diformazan
The methanol solution of yl acetamide solution and 4ml are uniformly mixed and obtain mixture；
S2, mixture is sealed in the stainless steel autoclave of tetrafluoroethene liner, then places stainless steel autoclave
In an oven, stainless steel autoclave be warming up to 100 DEG C from room temperature with 10 DEG C per hour, and mixture is stainless at 100 DEG C
Continuous heating 96 hours in steel autoclave；
After the completion of S3, heating, autoclave is cooled down with 5 DEG C per hour, after autoclave is cooled to room temperature, with N, N-
Dimethylacetylamide washs and isolates yellow crystals repeatedly, and yellow crystals are dried at room temperature for, and obtains three Vygens
Category-organic framework material, chemical molecular formula are： [Cd(ABTC)(H2O)2(DMA)] 4DMA, wherein ABTC are indicated：3,3 ',
5,5 '-azo benzene tertacarbonic acids, DMA table show：N,N-dimethylacetamide belongs to monoclinic system, space group P21/ c, structure cell ginseng
Number is α (°)=90, β (°)=
98.6970 (11), γ (°)=90, volumeYield is 65%.
1) crystal structure analysis
At 293k, single crystal X-ray diffraction number is had recorded using German Bruker Smart Apex II single crystal diffractometers
According to being radiated (λ=0.71069) using molybdenum target.Crystal separate unit includes two Cd2+, a ligand, two coordination H2O
Molecule and a coordination DMA molecule.Cd1 with come from four H47 oxygen atom ligands of ABTC ligands, Cd2+With from three
H4Three oxygen atoms of ABTC ligands, an oxygen atom for being coordinated DMA molecules and two coordination H2Two oxygen atoms of O molecules are matched
Position, as shown in Figure 2 a, Symmetry code:#1-x+1,y+0.5,-z+0.5；#2-x+1,-y+1,-z；#3x,-y+0.5,z-
0.5.Two kinds of Cd atoms are connect with carboxyl, form double-core [Cd2(CO)4(H2O)2(DMA)] cluster, adjacent cluster are mutually interconnected by ligand
It connects to form unlimited three-dimensional framework, as shown in Figure 2 b.Duct size observed by b axis is about WithIt is analyzed from topological angle, each double-core cluster is considered as 4 tie points, correspondingly, each H4ABTC matches
Body can also regard 4 tie points as, to form the pts topological structures (Fig. 2 c, 2d and 2e) of (4,4) connection.
2) powder x-ray diffraction (PXRD)
At 293k, it is tested, is surveyed using Rigaku model RINT Ultima III diffractometer
The angular range of examination is 3-60 °.As shown in figure 3, the PXRD spectrograms of simulation and the synthesis of crystal are identical good on key position
It is good, show it with good phase purity.
3) nitrogen adsorption
At 77K, the test of nitrogen adsorption isothermal curve is carried out using ASIQ (iQ-2) instrument.It is tested in gas absorption
Before, after 24 hours, methanol is filtered out in methyl alcohol for crystal immersion.Then, fresh methanol is added, then is removed after impregnating 24 hours
Remove nonvolatile solvent.Sample is collected after filtering, crystal is handled using similar method with dichloromethane, to remove methanol.It crosses
Crystal is collected after filter, and crystal is dried at room temperature for 12 hours.Before testing, " degassing " processing is carried out to crystal.Using
Brunauer-Emmett-Teller (Bet) method calculates specific surface area and pore volume, specific surface area 64m2·g-1.Using
Density functional theory (DFT) calculates pore size and pore-size distribution, the pore-size distribution schematic diagram of the crystal calculated are shown in Fig. 4 b.
4) liquid phase adsorption elemental iodine
Freshly prepd crystal 20mg is immersed in hexane solutions of the 3ml containing iodine, the iodine concentration in hexane solution is
4mg·mL-1, separated in time takes pictures to observe color change, and crystal becomes brown from initial yellow, finally becomes
For black.Meanwhile the variation of every section of time iodine solution concentration is monitored with UV absorption instrument, meanwhile, respectively at 1h, 4h, 8h,
18h, for 24 hours, the time point of 48h take out 100 microlitres of solution, dilute 100 times, measure its ultraviolet absorption curve.According to standard purple
Outer absorption curve calculates the quality of the adsorbent iodine of each time point and adsorbs the percentage that iodine quality accounts for solution iodine quality
Than, and dynamic analysis is carried out to adsorption process.Saturated extent of adsorption is 680mgg-1.Absorption curve in Fig. 5 c is from top to bottom
Respectively blank, 0min, 10min, 30min, 60min, 120min, 180min, 240min, 390min, 510min,
The corresponding 20mg crystal of 660min, 840min is in 0.4mgmL-1Ultra-violet absorption spectrum in the hexane solution of iodine.
5) Gas Phase Adsorption elemental iodine
By freshly prepd crystal 30mg and iodine in a closed container, take out at regular intervals sample into
Row is weighed, and registration to be weighed, which remains unchanged, calculates MOF to the saturation adsorptive value of iodine, saturated extent of adsorption 636.7mgg-1。
6) Dye Adsorption
Freshly prepd crystal 100mg is separately immersed in the DMA solution containing different charge dyestuffs (10 mL).It impregnates
Two days later, with DMA solution washing sample repeatedly, the dyestuff of remained on surface is removed.Crystal color have from yellow become green, because
This crystal can effectively adsorb dyestuff methylene blue (MB).Meanwhile methylene blue is adsorbed to crystal using ultra-violet absorption spectrum
Ability carry out quantitative analysis, the absorption curve in Fig. 6 a be respectively from top to bottom 0min, 5min, 15min, 30min,
The corresponding crystal of 60min, 100min, 120min, 150min, 180min, 210min, 240min, 270min, 300min is in DMA
The ultra-violet absorption spectrum of methylene blue dye is adsorbed in solution.
7) column chromatography dye separation
The rubber head dropper of rubber plug will be pulled out as the chromatographic column of pillar layer separation.Freshly prepd crystal is placed in chromatographic column
Interior, crystal need not carry out any activation process in advance.First, at room temperature, dyestuff methylene blue and Congo red will be mixed with
(1:1,1.0mmol) DMA solution passes through chromatographic column.Then, chromatographic column is washed repeatedly with pure DMA solution.Needed for being kept completely separate
Time be about 30 minutes or so, and with ultra-violet absorption spectrum come verify crystal detach dyestuff ability, as shown in fig. 7,
Crystal fills into column chromatography the photo record of separation methylene blue and congo red, and wherein I is crystal packed column, II-VI
For the color change of separation process, VII is to be kept completely separate, and crystal only adsorbs methylene blue.
Embodiment 2
S1, by the 3 of 0.015g, 3 ', 5,5 '-azo benzene tertacarbonic acids, the Cd (NO of 0.25g3)2·4H2O, the N of 4ml, N- bis-
The methanol solution of methyl vinyl amine aqueous solution and 4ml are uniformly mixed and obtain mixture；
S2, mixture is sealed in the stainless steel autoclave of tetrafluoroethene liner, then places stainless steel autoclave
In an oven, stainless steel autoclave is warming up to 110 DEG C from room temperature with 15 DEG C per hour, and mixture is stainless at 100-110 DEG C
Continuous heating 100 hours in steel autoclave；
After the completion of S3, heating, autoclave is cooled down with 7 DEG C per hour, after autoclave is cooled to room temperature, with N, N-
Dimethylacetylamide washs and isolates yellow crystals repeatedly, and yellow crystals are dried at room temperature for, and obtains three Vygens
Category-organic framework material.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understanding without departing from the principles and spirit of the present invention can carry out these embodiments a variety of variations, modification, replace
And modification, the scope of the present invention is defined by the appended.
Claims (9)
1. a kind of 3-dimensional metal-organic framework material, which is characterized in that chemical molecular formula is：[Cd(ABTC)(H2O)2
(DMA)] 4DMA, wherein ABTC are indicated：3,3 ', 5,5 '-azo benzene tertacarbonic acids, DMA table show：N,N-dimethylacetamide belongs to
In monoclinic system, space group P21/ c, cell parameter are α (°)=90, β (°)=98.6970
(11), γ (°)=90, volume
2. the preparation method of 3-dimensional metal-organic framework material described in claim 1, which is characterized in that include the following steps：
S1, by the 3 of 0.01-0.015g, 3 ', 5,5 '-azo benzene tertacarbonic acids, the Cd (NO of 0.20-0.25g3)2·4H2O、4-5mL
N,N-dimethylacetamide solution and 4-5mL methanol solution be uniformly mixed obtain mixture；
S2, mixture is sealed in the stainless steel autoclave of tetrafluoroethene liner, stainless steel autoclave is then placed on baking
In case, stainless steel autoclave is warming up to 100-110 DEG C from room temperature with 10-15 DEG C per hour, mixture at 100-110 DEG C not
Continuous heating 96-100 hours in rust steel autoclave；
After the completion of S3, heating, stainless steel autoclave is cooled down with 5-8 DEG C per hour, waits for that stainless steel autoclave is cooled to room temperature
Afterwards, it is washed repeatedly with n,N-dimethylacetamide and isolates yellow crystals, and yellow crystals are dried at room temperature for, obtained described
3-dimensional metal-organic framework material.
3. the preparation method of 3-dimensional metal-organic framework material as claimed in claim 2, which is characterized in that the step S1
In mixture by 3,3 ', 5, the 5 '-azo benzene tertacarbonic acids of 0.01g, the Cd (NO of 0.20g3)2·4H2O, the N of 4mL, N- diformazan
The methanol solution of yl acetamide solution and 4mL are mixed to get.
4. the preparation method of 3-dimensional metal-organic framework material as claimed in claim 2, which is characterized in that the step S2
Middle stainless steel autoclave is heated up since room temperature with 10 DEG C per hour.
5. the preparation method of 3-dimensional metal-organic framework material as claimed in claim 2, which is characterized in that the step S3
Middle stainless steel autoclave is cooled down with 5 DEG C per hour.
6. the application of 3-dimensional metal-organic framework material as described in claim 1, which is characterized in that the 3-dimensional metal-has
In terms of machine framework material is applied to waste liquid or exhaust-gas treatment containing elemental iodine.
7. the application of 3-dimensional metal-organic framework material as described in claim 1, which is characterized in that the 3-dimensional metal-has
In terms of machine framework material is applied to Dye Adsorption.
8. the application of 3-dimensional metal-organic framework material as claimed in claim 7, which is characterized in that the dyestuff is methylene
Base is blue.
9. the application of 3-dimensional metal-organic framework material as described in claim 1, which is characterized in that the 3-dimensional metal-has
Machine framework material is applied to column chromatography dye separation methylene blue and Congo red.
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| CN109467711A (en) * | 2018-11-01 | 2019-03-15 | 陕西科技大学 | A kind of novel C d coordination polymer iodine vapor support materials and the preparation method and application thereof |
| CN113185698A (en) * | 2021-05-20 | 2021-07-30 | 山西师范大学 | Preparation method and application of four-core cadmium cluster organic framework |
| CN113413770A (en) * | 2021-07-05 | 2021-09-21 | 富海(东营)新材料科技有限公司 | Preparation method and application of MOFs-PSU iodine load membrane |
| CN114751462A (en) * | 2022-03-17 | 2022-07-15 | 吉林师范大学 | Preparation method of Cd-MOF derivative material based on iron ion exchange and application of Cd-MOF derivative material in lithium ion battery cathode |
| CN115254061A (en) * | 2022-08-15 | 2022-11-01 | 齐齐哈尔大学 | Preparation method of ultrahigh cross-linked porous organic polymer iodine adsorbent |
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| CN109467711A (en) * | 2018-11-01 | 2019-03-15 | 陕西科技大学 | A kind of novel C d coordination polymer iodine vapor support materials and the preparation method and application thereof |
| CN113185698A (en) * | 2021-05-20 | 2021-07-30 | 山西师范大学 | Preparation method and application of four-core cadmium cluster organic framework |
| CN113185698B (en) * | 2021-05-20 | 2022-11-15 | 山西师范大学 | Preparation method and application of four-core cadmium cluster organic framework |
| CN113413770A (en) * | 2021-07-05 | 2021-09-21 | 富海(东营)新材料科技有限公司 | Preparation method and application of MOFs-PSU iodine load membrane |
| CN114751462A (en) * | 2022-03-17 | 2022-07-15 | 吉林师范大学 | Preparation method of Cd-MOF derivative material based on iron ion exchange and application of Cd-MOF derivative material in lithium ion battery cathode |
| CN114751462B (en) * | 2022-03-17 | 2023-10-03 | 吉林师范大学 | Preparation method of Cd-MOF derivative material based on iron ion exchange and application of derivative material in aspect of lithium ion battery cathode |
| CN115254061A (en) * | 2022-08-15 | 2022-11-01 | 齐齐哈尔大学 | Preparation method of ultrahigh cross-linked porous organic polymer iodine adsorbent |
| CN115254061B (en) * | 2022-08-15 | 2023-07-21 | 齐齐哈尔大学 | Preparation method of ultrahigh crosslinked porous organic polymer iodine adsorbent |
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