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 PDF

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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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张姝然
姚婵
徐广娟
柳志学
谢伟
许彦红
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Jilin Normal University
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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

A kind of 3-dimensional metal-organic framework material and its preparation method and application
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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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

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106967219A (en) * 2017-03-23 2017-07-21 山西师范大学 Cadmium metal organic framework materials based on 3,3 ', 5,5 ' biphenyltetracarboxyacid acids and its preparation method and application

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106967219A (en) * 2017-03-23 2017-07-21 山西师范大学 Cadmium metal organic framework materials based on 3,3 ', 5,5 ' biphenyltetracarboxyacid acids and its preparation method and application

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
BING MA ET AL: "Three metal-organic frameworks constructed from 3,3′,5,5′-azobenzene-tetracarboxylic acid: Synthesis, structure and luminescent sensing", 《INORGANICA CHIMICA ACTA》 *
CHAN YAO ET AL: "A multifunctional microporous metal–organic framework: efficient adsorption of iodine and column-chromatographic dye separation", 《RSC ADV.》 *
PEI-YAO DU ET AL: "Three types of lanthanide coordination polymers from 1D to 3D based on a tetracarboxylate ligand:synthesis, structural diversities and properties", 《CRYSTENGCOMM》 *
QING-FENG ZHANG ET AL: "Synthesis, Structure, and Characterization of a Microporous Metal-Organic Framework with PtS Topology", 《Z. ANORG. ALLG. CHEM.》 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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