CN108558918B - Three-dimensional metal-organic framework material and preparation method and application thereof - Google Patents
Three-dimensional metal-organic framework material and preparation method and application thereof Download PDFInfo
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- CN108558918B CN108558918B CN201810488414.1A CN201810488414A CN108558918B CN 108558918 B CN108558918 B CN 108558918B CN 201810488414 A CN201810488414 A CN 201810488414A CN 108558918 B CN108558918 B CN 108558918B
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- 239000000463 material Substances 0.000 title claims abstract description 29
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 48
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 29
- 239000010935 stainless steel Substances 0.000 claims abstract description 29
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011630 iodine Substances 0.000 claims abstract description 25
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 17
- MXBBZODCMBYDCL-UHFFFAOYSA-N 5-[(3,5-dicarboxyphenyl)diazenyl]benzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(C(=O)O)=CC(N=NC=2C=C(C=C(C=2)C(O)=O)C(O)=O)=C1 MXBBZODCMBYDCL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000007789 sealing Methods 0.000 claims abstract description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 239000003446 ligand Substances 0.000 claims description 9
- 239000002699 waste material Substances 0.000 claims description 5
- 239000003463 adsorbent Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 2
- 239000002912 waste gas Substances 0.000 claims description 2
- 239000000975 dye Substances 0.000 description 17
- 238000001179 sorption measurement Methods 0.000 description 17
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical group C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 14
- 229960000907 methylthioninium chloride Drugs 0.000 description 14
- 239000011148 porous material Substances 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- 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 description 5
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
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- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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Abstract
The invention discloses a three-dimensional metal-organic framework material and a preparation method and application thereof, belonging to the technical field of materials. The preparation method of the material comprises the following steps: s1, mixing 3, 3 ', 5, 5' -azobenzene tetracarboxylic acid and Cd (NO)3)2·4H2O, N mixing the N-dimethyl acetamide solution and the methanol solution to obtain a mixture; s2, sealing the mixture in a stainless steel autoclave with a tetrafluoroethylene lining, and continuously heating the mixture in the stainless steel autoclave at 100 ℃ for 96 hours; s3, cooling the stainless steel autoclave at 5 ℃ per hour, repeatedly washing the cooled stainless steel autoclave with N, N-dimethylacetamide to separate yellow crystals after the cooled stainless steel autoclave is cooled to room temperature, and drying the yellow crystals at room temperature to obtain the three-dimensional metal-organic framework material with the chemical formula of [ Cd2(ABTC)(H2O)2(DMA)]4 DMA. The crystal prepared by the invention can effectively adsorb elemental iodine and dye.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a three-dimensional metal-organic framework material and a preparation method and application thereof.
Background
With the rapid development of modern society and the continuous progress of science and technology, the release amount of dangerous chemicals such as nuclear waste, toxic heavy metal ions, organic dye components is increasing, which poses a significant threat to the health and safety of human beings and animals. Despite the rapidly increasing demand for efficient and carbon-emission-free nuclear energy, the approach to the disposal of waste from uranium nuclear fission is a safety issue of urgent concern behind nuclear power production. In particular radioactive iodine (containing129I and/or131I) As a major component of nuclear waste, considerable attention has been paid, mainly because it can cause serious tissue damage and canceration to human health via the respiratory system. In addition to this, in the case of a single-layer,129i and131the radioactive half-lives of I were 8 days and 1.57 × 10, respectively7Can slowly permeate into the metabolic system of the human body in years. Therefore, designing stable and efficient radioactive iodine capture and storage materials has become an urgent problem to be solved. Thus, it is crucial to synthesize highly efficient, low cost, stable porous materials for iodine capture in both gas and liquid phases. Among many porous materials, Metal-Organic Frameworks (MOFs) have been studied very abundantly, mainly because of their high specific surface area, adjustable pore structure, regular pore patterns, unique structure and powerful functions. In addition, the organic ligands with different geometric configurations and functions are selected to be coordinated with metal ions or clusters, MOFs with high porosity and adjustable pore structures can be obtained, and the structural characteristics are favorable for forming ideal surface binding sites and are favorable for capturing iodine.
Secondly, organic dyes are widely applied to industrial fields such as papermaking, printing, plastics, textiles, medicine and the like, but toxicity and even carcinogenicity of the organic dyes form great threats to water environment and human health. Meanwhile, most dyes are difficult to degrade due to their good stability to light and oxidizing agents. Therefore, a low-cost and environmentally friendly dye adsorption separation material is urgently needed.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a three-dimensional metal-organic framework material, and a preparation method and application thereof.
The invention relates to a three-dimensional metal-organic framework material, which has the chemical molecular formula: [ Cd ]2(ABTC)(H2O)2(DMA)]4DMA, where ABTC represents: 3, 3 ', 5, 5' -azobenzene tetracarboxylic acid ligand deprived of 4 protons, DMA represents: n, N-dimethylacetamide belonging to the monoclinic system having the space group ofP21/cCell parameter ofa(Å) = 14.3590(9)，b(Å)= 14.4350(10)，c(Å) = 22.6110(14)，α(°) = 90，β(°) = 98.6970(11)，γ(°) = 90, volumeV(Å3) = 4632.7 (5); the three-dimensional metal-organic framework material is used as an adsorbent to be applied to the treatment of the iodine-containing waste liquid or waste gas.
The invention also provides a preparation method of the three-dimensional metal-organic framework material, which comprises the following steps:
s1, mixing 0.01-0.015g of 3, 3 ', 5, 5' -azobenzene tetracarboxylic acid and 0.20-0.25g of Cd (NO)3)2·4H2O, N-dimethylacetamide solution of 4-5m L and methanol solution of 4-5m L are mixed uniformly to obtain a mixture;
s2, sealing the mixture in a stainless steel autoclave with a tetrafluoroethylene lining, then placing the stainless steel autoclave in an oven, raising the temperature of the stainless steel autoclave from room temperature to 110 ℃ at 10-15 ℃ per hour, and continuously heating the mixture in the stainless steel autoclave at 110 ℃ for 96-100 hours;
s3, after heating, cooling the stainless steel autoclave at 5-8 ℃ per hour, repeatedly washing the stainless steel autoclave to room temperature by using N, N-dimethylacetamide to separate out yellow crystals, and drying the yellow crystals at room temperature to obtain the three-dimensional metal-organic framework material.
Preferably, the mixture in step S1 is composed of 0.01g of 3, 3 ', 5, 5' -azobenzene tetracarboxylic acid, 0.20g of Cd (NO)3)2·4H2O, 4m L solution in N, N-dimethylacetamide and 4m L solution in methanolMixing the solutions.
Preferably, the stainless steel autoclave in step S2 is warmed up from room temperature at 10 ℃ per hour.
Preferably, the stainless steel autoclave in step S3 is cooled at 5 ℃ per hour.
The three-dimensional metal-organic framework material is applied to dye adsorption.
Preferably, the dye is methylene blue.
The three-dimensional metal-organic framework material is applied to separating methylene blue and Congo red by column chromatography dyes.
Compared with the prior art, the invention has the beneficial effects that: the invention reasonably designs and synthesizes a three-dimensional microporous crystal under the condition of solvothermal reaction. The crystal has microporous structure, can capture neutral iodine molecules in liquid phase and gas phase, and has remarkable adsorption capacity, and saturated adsorption capacity in liquid phase is 680 mg g-1. A series of qualitative and quantitative analysis methods are adopted to analyze the adsorption kinetics in the iodine adsorption process. The crystal prepared by the invention can be used for selectively adsorbing methylene blue and can also be used for separating methylene blue and Congo red by column chromatography dye. Therefore, the crystal is an effective adsorbent and can effectively adsorb the elemental iodine and the dye.
Drawings
FIG. 1 shows the present invention H4A schematic structural diagram of ABTC;
FIG. 2(a) is a schematic diagram of the coordination structure of the crystal of the present invention.
FIG. 2(b) is a three-dimensional cell structure in the b-axis direction according to the present invention;
FIGS. 2(c) and 2(d) are schematic diagrams of a club and a polyhedron of the connection topology of the present invention (4, 4);
FIG. 2(e) is a schematic diagram of a tile structure of the (4,4) connection topology of the present invention.
FIG. 3 is a PXRD spectrum of crystal simulation and synthesis of the present invention;
FIG. 4(a) is a plot of nitrogen adsorption and desorption isotherms of crystals of the present invention measured at 77K, 1 atm;
FIG. 4(b) is a diagram illustrating the pore size distribution of the crystal calculated by the density functional theory according to the present invention;
FIG. 5(a) shows the process of adsorbing iodine in n-hexane and releasing iodine in ethanol by the crystal of the present invention;
FIG. 5(b) shows the color change process of the crystal of the present invention during the absorption and release of iodine;
FIG. 5(c) shows that 20 mg of the crystal of the present invention is present at 0.4 mg. m L-1Ultraviolet absorption spectra in iodine in n-hexane solution;
FIG. 6(a) is the UV absorption spectrum of the crystal of the present invention adsorbing methylene blue dye in DMA solution;
FIG. 6(b) is a photograph of the color change of the crystal of the present invention after adsorbing methylene blue dye for a period of time;
FIG. 7 is a photographic record of the separation of methylene blue and Congo red dyes in a column chromatography packed with crystals of the present invention.
Detailed Description
Detailed description of the preferred embodimentsthe following detailed description of the present invention will be given with reference to the accompanying drawings 1-7, but it should be understood that the scope of the present invention is not limited to the specific embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
S1, mixing 0.01g of 3, 3 ', 5, 5' -azobenzene tetracarboxylic acid and 0.2g of Cd (NO)3)2·4H2O, 4ml of N, N-dimethylacetamide solution and 4ml of methanol solution are mixed evenly to obtain a mixture;
s2, sealing the mixture in a stainless steel autoclave with a tetrafluoroethylene lining, then placing the stainless steel autoclave in an oven, heating the stainless steel autoclave from room temperature to 100 ℃ at 10 ℃ per hour, and continuously heating the mixture in the stainless steel autoclave at 100 ℃ for 96 hours;
s3, after the heating is finished, the temperature of the high-pressure autoclave is reduced by 5 ℃ per hour, and after the high-pressure autoclave is cooled to the room temperature, the high-pressure autoclave is repeatedly washed and separated by N, N-dimethylacetamideAnd (3) separating out yellow crystals, and drying the yellow crystals at room temperature to obtain the three-dimensional metal-organic framework material, wherein the chemical molecular formula of the three-dimensional metal-organic framework material is as follows: [ Cd ]2(ABTC)(H2O)2(DMA)]4DMA, where ABTC represents: 3, 3 ', 5, 5' -azobenzene tetracarboxylic acid ligand deprived of 4 protons, DMA represents: n, N-dimethylacetamide belonging to the monoclinic system having the space group ofP21/cCell parameter ofa(Å) = 14.3590(9)，b(Å) = 14.4350(10)，c(Å) = 22.6110(14)，α(°) = 90，β(°) = 98.6970(11)，γ(°) = 90, volumeV(Å3) = 4632.7(5), yield 65%.
1) Analysis of crystal structure
Single crystal X-ray diffraction data were recorded at 293K using a Bruker Smart Apex II single crystal diffractometer in germany, irradiated with a molybdenum target (λ = 0.71069). The crystal independent unit contains two Cd2+One ligand, two ligands H2An O molecule and one coordinating DMA molecule. Cd1 with H from four4Coordination of 7 oxygen atoms of the ABTC ligand, Cd2+And from three H4Three oxygen atoms of the ABTC ligand, one oxygen atom of the coordinating DMA molecule, and two coordinating H2Two oxygen atoms of the O molecule are coordinated as shown in FIG. 2a, Symmetry code: # 1-x +1, y +0.5, -z +0.5, # 2-x +1, -y +1, -z, #3 x, -y +0.5, z-0.5. Two Cd atoms are connected with carboxyl to form binuclear [ Cd2(COO)4(H2O)2(DMA)]Clusters, adjacent clusters interconnected by ligands to form an infinite three-dimensional framework, as shown in FIG. 2b, and a tunnel size, as viewed along the b-axis, of about 10.4 × 8.7.7 8.7 Å2And 7.8 × 7.5 Å2. From a topological point of view, each dual-core cluster can be regarded as a 4-connection point, and accordingly, each H4The ABTC ligand can also be viewed as a 4-point of attachment, thus forming a (4,4) -linked pts topology (fig. 2c, 2d and 2 e).
2) Powder X-ray diffraction (PXRD)
The tests were carried out at 293K using a Rigaku model RINT Ultima III diffractometer, the angular range of the tests being 3-60 °. As shown in fig. 3, the simulated and synthesized PXRD patterns of the crystals matched well at key locations, indicating that they had good phase purity.
3) Adsorption of nitrogen
The nitrogen adsorption isotherm curve was tested at 77K using an ASIQ (iQ-2) instrument. After soaking the crystals in methanol for 24 hours before the gas adsorption test, the methanol was filtered off. Then, fresh methanol was added, and after soaking for another 24 hours, the nonvolatile solvent was removed. After filtration, a sample was collected and the crystals were treated with dichloromethane in a similar manner to remove methanol. After filtration, the crystals were collected and dried at room temperature for 12 hours. Prior to testing, the crystals were "degassed". The specific surface area and pore volume were calculated by the method of Brunauer-Emmett-Teller (bet) and the specific surface area was 64 m2·g-1. The pore size and pore size distribution were calculated using the Density Functional Theory (DFT) and the calculated pore size distribution of the crystal is schematically shown in fig. 4 b.
4) Liquid phase adsorption of iodine simple substance
Soaking 20 mg of the newly prepared crystal in 3ml of iodine-containing n-hexane solution with iodine concentration of 4 mg. m L-1Photographs were taken at regular intervals to observe the color change, with the crystals changing from initially yellow to brown and finally to black. Meanwhile, the change of the concentration of the iodine solution in each period of time is monitored by an ultraviolet absorption instrument, and simultaneously, 100 microliters of the solution is taken out at the time points of 1h, 4h, 8h, 18h, 24h and 48h respectively, diluted by one hundred times and the ultraviolet absorption curve of the solution is measured. And calculating the mass of the iodine adsorbed by the adsorbent at each time point and the percentage of the adsorbed iodine mass to the solution iodine mass according to the standard ultraviolet absorption curve, and performing kinetic analysis on the adsorption process. The saturated adsorption capacity was 680 mg g-1The absorption curves in FIG. 5c are from top to bottom 20 mg crystals at 0.4 mg. m L for blank, 0min, 10min, 30min, 60min, 120min, 180min, 240min, 390min, 510min, 660min, 840min, respectively-1Ultraviolet absorption spectrum in iodine in n-hexane solution.
5) Gas phase adsorption of iodine simple substance
30 mg of newly prepared crystal and elementary iodine are put in a closed container, and samples are taken out at regular intervalsWeighing the product, and calculating the saturated adsorption value of MOF to iodine with the saturation adsorption amount of 636.7 mg g-1。
6) Dye adsorption
The method comprises the steps of respectively soaking 100 mg of newly prepared crystals in DMA solutions (10 m L) containing dyes with different charges for two days, repeatedly washing the samples by the DMA solutions to remove the dyes remained on the surfaces, wherein the colors of the crystals are changed from yellow to green, so that the crystals can effectively adsorb the dye Methylene Blue (MB), and simultaneously, the capacity of the crystals for adsorbing the methylene blue is quantitatively analyzed by using an ultraviolet absorption spectrum, and the absorption curves in the graph of fig. 6a are respectively 0min, 5min, 15min, 30min, 60min, 100min, 120min, 150min, 180min, 210min, 240min, 270min and 300min from top to bottom, and the ultraviolet absorption spectra of the methylene blue dyes are adsorbed by the crystals in the DMA solutions.
7) Column chromatography dye separation
The rubber head dropper with the rubber plug removed is used as a chromatographic column for column chromatographic separation. The freshly prepared crystals are placed in a chromatographic column without any prior activation of the crystals. First, a DMA solution mixed with the dyes methylene blue and Congo Red (1:1, 1.0 mmol) was passed through a chromatography column at room temperature. The column was then washed repeatedly with pure DMA solution. The time required for complete separation was approximately 30 minutes and the ability of the crystals to separate the dyes was verified by UV absorption spectroscopy, as shown in FIG. 7, the photographic record of the separation of methylene blue and Congo red dyes in a column chromatography with crystals packed in I, column, II-
In order to effect a color change in the separation process,
for complete separation, the crystals adsorb only methylene blue.
Example 2
S1, 0.015g of 3, 3 ', 5, 5' -azobenzene tetracarboxylic acid and 0.25g of Cd (NO)3)2·4H2O, 4ml of N, N-dimethylacetamide solution and 4ml of methanol solutionMixing uniformly to obtain a mixture;
s2, sealing the mixture in a stainless steel autoclave with a tetrafluoroethylene lining, then placing the stainless steel autoclave in an oven, raising the temperature of the stainless steel autoclave from room temperature to 110 ℃ at 15 ℃ per hour, and continuously heating the mixture in the stainless steel autoclave at the temperature of 100 ℃ and 110 ℃ for 100 hours;
s3, after heating, cooling the autoclave at 7 ℃ per hour, repeatedly washing and separating yellow crystals by using N, N-dimethylacetamide after the autoclave is cooled to room temperature, and drying the yellow crystals at room temperature to obtain the three-dimensional metal-organic framework material.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (5)
1. The application of a three-dimensional metal-organic framework material is characterized in that the chemical formula of the three-dimensional metal-organic framework material is as follows: [ Cd ]2(ABTC)(H2O)2(DMA)]4DMA, where ABTC represents: 3, 3 ', 5, 5' -azobenzene tetracarboxylic acid ligand deprived of 4 protons, DMA represents: n, N-dimethylacetamide belonging to monoclinic system with space group P21C, unit cell parameter of
α (deg.) 90, β (deg.) 98.6970(11), γ (deg.) 90, volume
The three-dimensional metal-organic framework material is used as an adsorbent to be applied to the treatment of the iodine-containing waste liquid or waste gas.
2. Use of a three-dimensional metal-organic framework material according to claim 1, characterized in that the preparation process of said three-dimensional metal-organic framework material comprises the following steps:
s1, mixing 0.01-0.015g of 3, 3 ', 5, 5' -azobenzene tetracarboxylic acid and 0.20-0.25g of Cd (NO)3)2·4H2O, N-dimethylacetamide solution of 4-5m L and methanol solution of 4-5m L are mixed uniformly to obtain a mixture;
s2, sealing the mixture in a stainless steel autoclave with a tetrafluoroethylene lining, then placing the stainless steel autoclave in an oven, raising the temperature of the stainless steel autoclave from room temperature to 110 ℃ at 10-15 ℃ per hour, and continuously heating the mixture in the stainless steel autoclave at 110 ℃ for 96-100 hours;
s3, after heating, cooling the stainless steel autoclave at 5-8 ℃ per hour, repeatedly washing the stainless steel autoclave to room temperature by using N, N-dimethylacetamide to separate out yellow crystals, and drying the yellow crystals at room temperature to obtain the three-dimensional metal-organic framework material.
3. Use of a three-dimensional metal-organic framework material according to claim 2, wherein the mixture in step S1 of the preparation method of the three-dimensional metal-organic framework material is prepared from 0.01g of 3, 3 ', 5, 5' -azobenzene tetracarboxylic acid, 0.20g of Cd (NO)3)2·4H2O, 4m L solution in N, N-dimethylacetamide and 4m L solution in methanol.
4. Use of a three-dimensional metal-organic framework material according to claim 2, wherein the stainless steel autoclave is warmed at 10 ℃ per hour from room temperature in step S2.
5. Use of a three-dimensional metal-organic framework material according to claim 2, wherein the stainless steel autoclave is cooled at 5 ℃ per hour in step S3.
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