CN115703887B - Zn-MOF-74 metal organic framework material, preparation and application thereof in toluene adsorption - Google Patents
Zn-MOF-74 metal organic framework material, preparation and application thereof in toluene adsorption Download PDFInfo
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000013115 Zn-MOF-74 Substances 0.000 title claims abstract description 61
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 title claims abstract description 23
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims abstract description 46
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 36
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 20
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000012046 mixed solvent Substances 0.000 claims abstract description 11
- 239000012456 homogeneous solution Substances 0.000 claims abstract description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000001291 vacuum drying Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims description 13
- 238000004321 preservation Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 4
- 239000013078 crystal Substances 0.000 abstract description 38
- 229910021642 ultra pure water Inorganic materials 0.000 abstract description 16
- 239000012498 ultrapure water Substances 0.000 abstract description 16
- 239000002341 toxic gas Substances 0.000 abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 2
- 239000001569 carbon dioxide Substances 0.000 abstract description 2
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 description 11
- 239000011701 zinc Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000013118 MOF-74-type framework Substances 0.000 description 5
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- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000012795 verification Methods 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000002178 crystalline material Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
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- 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
- 208000007443 Neurasthenia Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- XYVDNBKDAAXMPG-UHFFFAOYSA-M decyl 2-(1-heptylazepan-1-ium-1-yl)acetate;hydroxide Chemical compound [OH-].CCCCCCCCCCOC(=O)C[N+]1(CCCCCCC)CCCCCC1 XYVDNBKDAAXMPG-UHFFFAOYSA-M 0.000 description 1
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- 230000004580 weight loss Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
The invention provides a preparation method of a Zn-MOF-74 porous metal organic framework material applied to toluene adsorption, which comprises the following steps: 1) Dissolving a certain amount of zinc nitrate and 2, 5-dihydroxyterephthalic acid (DHTA) in a mixed solvent of N, N-dimethylformamide DMF, absolute ethanol and ultrapure water, and then performing ultrasonic treatment on the obtained mixture solution to obtain a homogeneous solution; 2) Transferring the solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, placing the high-pressure reaction kettle into an oven for preserving heat for a certain time, cooling the high-pressure reaction kettle to room temperature, and centrifugally collecting a product; 3) Washing with DMF and methanol for several times, vacuum drying to obtain Zn-MOF-74 crystal, taking out and storing for use. The obtained Zn-MOF-74 crystal not only has high stability, but also has a hexagonal honeycomb network topology structure, and a large specific surface area and rich porosity are provided for the Zn-MOF-74 crystal. In addition to exhibiting high adsorptivity to water vapor and carbon dioxide, toxic gases such as p-toluene also exhibit excellent adsorptivity.
Description
Technical Field
The invention relates to the field of toxic gas purification, in particular to a toxic gas toluene adsorbent and a preparation method thereof.
Background
As early as 2017, the world health organization international cancer research institute has listed toluene as a carcinogen. The average concentration of air in many cities around the world is summarized, and the result shows thatToluene concentration is generally 112.5-150. Mu.g/m 3 This comes mainly from emissions associated with gasoline, as well as from solvent losses and emissions from industrial activities. It has serious harm to environment and pollution to air and water source; in addition, the traditional Chinese medicine composition has serious influence on human health, has irritation to skin and mucous membrane, has anesthetic effect on a central nervous system, and can generate neurasthenia syndrome after long-term contact.
At present, the existing gas purification mode generally adopts physical adsorption of active carbon, natural zeolite and the like, but the adsorption quantity of the material is smaller, the consumption is larger, the adsorption capacity is not strong, and the adsorption quantity is reduced or even the adsorption capacity is lost after a certain period of use. In addition, the adsorption specificity problem exists in the adsorption process, the adsorption performance of the mixed gas is weakened, and the desorption phenomenon caused by the mismatch of the molecular diameter and the pore diameter of the adsorbed substances exists. In addition, the natural zeolite pore canal is easy to be blocked, the surface silica structure of the natural zeolite pore canal has extremely strong hydrophilicity, and anions outside the structure are easy to hydrolyze.
Metal-organic frameworks (Metal-Organic Frameworks, MOFs) are novel multifunctional materials for the 21 st century. The metal ions and the organic ligands are connected together through coordination bonds, and a honeycomb-like regular and ordered network structure is formed after connection, and the structure is various and adjustable. Because of the relatively strong forces of coordination bonds, MOFs generally have a more stable structure than other supramolecular systems constructed with weak interactions. Compared with the traditional inorganic zeolite material and porous carbon material, the MOFs material has higher porosity and larger specific surface area, can be used as a novel active gas adsorption material, and has larger application potential in the field of environmental protection.
Disclosure of Invention
Among the many MOFs materials, MOF-74 is known for structural stability. When the environment where the structures of the common MOFs are positioned changes, the structures of the common MOFs are easily damaged, so that the adsorption quantity of the common MOFs to the gas is reduced. However, MOF-74 is excellent in stability and the structure is not greatly affected by environmental changes. The open metal sites form an angled complex with the adsorbed molecules. Through physical and chemical adsorption, a better treatment effect is achieved.
Aiming at the prior problems, the invention provides a preparation method of a Zn-MOF-74 porous metal organic framework material applied to toluene adsorption, which aims at solving the technical problems: zinc nitrate and 2, 5-dihydroxyterephthalic acid (DHTA) were dissolved in a mixed solvent of N, N-dimethylformamide DMF, absolute ethanol and ultrapure water, the resulting mixture solution was sonicated, then transferred to an autoclave lined with polytetrafluoroethylene for a certain period of time, then cooled to room temperature, and the product was collected by centrifugation. Washing with DMF and methanol several times, and then vacuum drying gave Zn-MOF-74 crystals.
The technical scheme adopted by the invention for solving the technical problems is as follows: the preparation method of the Zn-MOF-74 porous metal-organic framework material applied to toluene adsorption is characterized by comprising the following steps in sequence:
1) Dissolving a certain amount of zinc nitrate and 2, 5-dihydroxyterephthalic acid (DHTA) in a mixed solvent of N, N-dimethylformamide DMF, absolute ethanol and ultrapure water, and then performing ultrasonic treatment on the obtained mixture solution to obtain a homogeneous solution;
2) Transferring the solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, placing the high-pressure reaction kettle into an oven for preserving heat for a certain time, cooling the high-pressure reaction kettle to room temperature, and centrifugally collecting a product;
3) Washing several times with DMF and methanol followed by vacuum drying gives Zn-MOF-74 material that can be applied to toluene adsorption.
According to the scheme, the molar ratio of the zinc nitrate to the 2, 5-dihydroxyterephthalic acid in the step 1) is 1-4.
According to the scheme, the volume ratio of the N, N-dimethylformamide DMF, the absolute ethyl alcohol and the ultrapure water in the step 1) is 1-3:1:1-0.
According to the scheme, the ultrasonic treatment time of the mixture solution in the step 1) is 5-20min.
According to the scheme, the heat preservation temperature in the step 2) is 100-150 ℃, and the heat preservation time is 12-24h.
According to the scheme, the centrifugal rotating speed in the step 2) is 2000-8000r/min, and the centrifugal time is 5-10min.
According to the above scheme, the number of washes with DMF and methanol as described in step 3) is 3-6.
According to the scheme, the temperature of the vacuum drying in the step 3) is 60-80 ℃, and the drying time is 6-12h.
The invention provides a method for synthesizing Zn-MOF-74 by a hydrothermal method, wherein the Zn-MOF-74 crystal is finally obtained by adjusting the proportion of a solvent and a solute and controlling the growth process of the crystal.
Microstructure characterization method of Zn-MOF-74 crystal: the material crystal structure was analyzed by X-ray diffraction (XRD) spectroscopy, the morphology of the material was observed by Scanning Electron Microscopy (SEM), the thermal stability of the sample was analyzed by thermogravimetric analysis (TGA), the pore size and specific surface area of the sample were analyzed by BET, and the elemental composition of the material was analyzed by energy spectroscopy (EDS).
The invention has the beneficial effects that: the Zn-MOF-74 porous metal organic framework material is synthesized by a simple hydrothermal method, and has the advantages of simple synthesis process and convenient operation. By optimizing the synthesis conditions, zn-MOF-74 crystal with better performance is synthesized, and the specific surface area can reach 866m 2 And/g. The adsorption capacity of toxic gases harmful to the environment and the health of human bodies, such as toluene, can reach 308 mg.g -1 . The invention has the advantages of low equipment requirement, no need of expensive various reaction devices, easy mass synthesis and the like, and is expected to generate good social and economic benefits.
The obtained Zn-MOF-74 crystal not only has high stability, but also has a hexagonal honeycomb network topology structure, and a large specific surface area and rich porosity are provided for the Zn-MOF-74 crystal. In addition to exhibiting high adsorptivity to water vapor and carbon dioxide, toxic gases such as p-toluene also exhibit excellent adsorptivity. The adsorption of Zn-MOF-74 to toluene is mainly derived from Van der Waals and electrostatic forces between toluene and metal sites, and toluene is mainly adsorbed on the metal sites and forms a complex with metal atoms at an angle.
Drawings
FIG. 1 is a toluene adsorption curve of Zn-MOF-74 crystals in example 1;
FIG. 2 is an XRD pattern of Zn-MOF-74 crystals in example 1;
FIG. 3 is an SEM image of Zn-MOF-74 crystals of examples 1, 2, 3, 4, 5;
wherein: a) Zn-MOF-74 (V) DMF :V Absolute ethyl alcohol :V Ultrapure water ＝1:1:1，n Zn(NO3)2·6H2O :n DHTA ＝1:1)；
b)Zn-MOF-74(V DMF :V Absolute ethyl alcohol :V Ultrapure water ＝1:1:1，n Zn(NO3)2·6H2O :n DHTA ＝2:1)；
c)Zn-MOF-74(V DMF :V Absolute ethyl alcohol :V Ultrapure water ＝1:1:1，n Zn(NO3)2·6H2O :n DHTA ＝3:1)；
d)Zn-MOF-74(V DMF :V Absolute ethyl alcohol :V Ultrapure water ＝1:1:0，n Zn(NO3)2·6H2O :n DHTA ＝3:1)；
e)Zn-MOF-74(V DMF :V Absolute ethyl alcohol :V Ultrapure water ＝3:1:1，n Zn(NO3)2·6H2O :n DHTA ＝3:1).
FIG. 4 is a TG curve of Zn-MOF-74 crystals of example 1;
FIG. 5 is N of Zn-MOF-74 crystals in example 1 2 Adsorption-desorption curves;
table 1 shows the EDS elemental analysis of Zn-MOF-74 crystals in example 1;
table 2 shows the pore structure parameters of the Zn-MOF-74 crystals in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples, but the present invention is not limited thereto.
Example 1:
3.2145g of zinc nitrate hexahydrate Zn (NO) 3 ) 2 ·6H 2 O and 0.7369g of 2, 5-dihydroxyterephthalic acid (DHTA) are mixed and dissolved in a mixed solvent of 10mL of N, N-dimethylformamide DMF, 10mL of absolute ethyl alcohol and 10mL of ultrapure water, and the resulting mixture solution is sonicated for about 10 minutes to become a homogeneous solution, and then the solution is transferred to an autoclave lined with polytetrafluoroethylene and placed in an oven at 100 DEG CFor a period of 24 hours. After cooling to room temperature, the pale yellow product was collected by centrifugation at 5000r/min for 5min, and finally washed successively with DMF and methanol 2 times each, and then dried under vacuum at 60℃for 12h to give Zn-MOF-74 as yellow crystals.
FIG. 1 is a Zn-MOF-74 toluene adsorption curve. Vacuum drying at 60deg.C for 6 hr under Zn-MOF-74 pretreatment condition, testing temperature 25deg.C, toluene vapor at relative pressure P/P 0 In the whole range of the pressure of (P0 is standard atmospheric pressure), the adsorption quantity of Zn-MOF-74 material to toluene is gradually increased, and the saturated adsorption quantity can reach 308 mg.g -1 The adsorption of Zn-MOF-74 to toluene is mainly derived from Van der Waals and electrostatic forces between toluene and metal sites, and toluene is mainly adsorbed on the metal sites and forms an angled complex with metal atoms.
FIG. 2 is an XRD pattern of Zn-MOF-74 crystals. The Zn-MOF-7 crystal has obvious diffraction peaks at the 2 theta=6.737 DEG position and the 2 theta= 11.698 DEG position, which are the same as the peak shape and position of the diffraction peak of the MOF-74 reported before, and the structure of the M-MOF-74 is not affected although the pattern has a small amount of miscellaneous peaks.
FIG. 3 is an SEM image of Zn-MOF-74 crystals. Respectively different solute ratios (the solvents are DMF: absolute ethanol: ultrapure water=1:1:1), different solvent ratios (the solutes are Zn (NO) in molar ratio 3 ) 2 ·6H 2 O dhta=3:1) Zn-MOF-74. As can be seen from the graph, the crystal morphology with the solute ratio of 3:1 is best, and to a certain extent, the crystal morphology can directly influence the crystal performance, which indicates that Zn (NO 3 )·6H 2 The excess of O can favor crystallization of the product Zn-MOF-74, while it can also be stated that the excess of ligand DHTA is detrimental to crystallization. From the figure, it can be seen that the morphology of Zn-MOF-74 materials prepared under different solvent ratio conditions is not quite different, which indicates that DMF contributes to the dissolution of DHTA, but excessive DMF does not contribute to the growth of crystals. For this reason, during the synthesis we have to choose the appropriate solute ratio, and also the appropriate DMF solvent.
FIG. 4 is a TG curve of Zn-MOF-74 crystals at N 2 Heating rate of 10 DEG min under atmosphere -1 The range is 40-800 ℃. Zn-MOF-74 has a relatively large weight loss before 100 ℃, which is caused by evaporation OF water molecules in the pore canal; the quality is basically unchanged between 100 ℃ and 300 ℃; further mass reduction of Zn-MOF-74 occurs after 300℃due to ligand to metal coordination bond cleavage, and collapse of Zn-MOF-74 structure.
FIG. 5 is N of Zn-MOF-74 crystal 2 Adsorption-desorption curve, degassing temperature 100 ℃, degassing time 120min, ambient temperature 20 ℃, adsorbate N 2 . In the low-pressure region (P/P 0 =0-0.1), the adsorption of nitrogen gas quickly reaches a saturation amount of 200cm 3 /g; in the medium-pressure region (P/P 0 =greater than 0.1 to 0.8), the degree of change in the amount of adsorbed nitrogen with increasing pressure is almost negligible; but when reaching the high pressure region (P/P 0 =greater than 0.8 to 1), the adsorption amount of nitrogen increases rapidly with pressure. From the figure it can be seen that the adsorption curve is substantially identical to the desorption curve, but that there is still a slight delay in the adsorption curve compared to the desorption curve of nitrogen in the high pressure region, which is probably due to the presence of some macropores in the Zn-MOF-74 crystalline material.
Table 1 shows the EDS elemental analysis of Zn-MOF-74 crystals, with Zn content only about 15%, carbon content up to about 63%, oxygen content about 21%, and carbon, zinc, oxygen content ratio about 12:3:4.
Table 2 shows pore structure parameters of Zn-MOF-74 crystals, wherein the mesoporous diameter of Zn-MOF-74 crystals is about 11nm, and the BET single point specific surface area is about 866m 2 Specific surface area of Langmuir method per gram is about 942m 2 And/g, the vacuum drying time is prolonged to remove guest molecules (water molecules) in the pores, and the specific surface area is slightly increased.
Table 1 list of the contents of elements in Zn-MOF-74
TABLE 2 pore Structure parameters of Zn-MOF-74 crystals
The pore diameter of the mesopores ranges from 2nm to 50nm, and the pore diameter of the micropores ranges from less than 2nm;
example 2:
to examine the effect of solute ratios on Zn-MOF-74 crystalline material, the solute ratio, namely zinc nitrate hexahydrate Zn (NO 3 ) 2 ·6H 2 The molar ratio of O to 2, 5-dihydroxyterephthalic acid is 2:1, and the reaction process is as follows: 2.1430g of zinc nitrate hexahydrate Zn (NO) 3 ) 2 ·6H 2 O and 0.7369g of 2, 5-dihydroxyterephthalic acid (DHTA) were mixed and dissolved in a mixed solvent of 10mL of N, N-dimethylformamide DMF, 10mL of absolute ethanol and 10mL of ultrapure water, and then the resulting mixture solution was sonicated for about 10 minutes to become a homogeneous solution, and then the solution was transferred to an autoclave lined with polytetrafluoroethylene and placed in an oven at 100℃for 24 hours. Then cooling the mixture to room temperature, centrifuging the mixture for 5min through 5000r/min, collecting a pale yellow product, washing the product with DMF and methanol for 2 times, and then drying the product in vacuum at 60 ℃ for 12h, thus obtaining Zn-MOF-74 yellow crystals through XRD verification.
Example 3:
to examine the effect of solute ratios on Zn-MOF-74 crystalline material, the solute ratio, namely zinc nitrate hexahydrate Zn (NO 3 ) 2 ·6H 2 The mol ratio of O to 2, 5-dihydroxyterephthalic acid is 1:1, and the reaction process is as follows: 1.0715g of zinc nitrate hexahydrate Zn (NO) 3 ) 2 ·6H 2 O and 0.7369g of 2, 5-dihydroxyterephthalic acid (DHTA) were mixed and dissolved in a mixed solvent of 10mL of N, N-dimethylformamide DMF, 10mL of absolute ethanol and 10mL of ultrapure water, and then the resulting mixture solution was sonicated for about 10 minutes to become a homogeneous solution, and then the solution was transferred to an autoclave lined with polytetrafluoroethylene and placed in an oven at 100℃for 24 hours. Then cooling to room temperature, and collecting the light by centrifugation at 5000r/min for 5minAnd finally, washing the yellow product with DMF and methanol for 2 times respectively, and then drying the yellow product in vacuum at 60 ℃ for 12 hours, thereby obtaining Zn-MOF-74 yellow crystals through XRD verification.
Example 4:
in order to examine the effect of the solvent on the Zn-MOF-74 crystal material, the volume ratio of the solvent, namely N, N-dimethylformamide DMF, absolute ethyl alcohol and ultrapure water, was changed to be 1:1:0, and the reaction process is as follows: 3.2145g of zinc nitrate hexahydrate Zn (NO) 3 ) 2 ·6H 2 O and 0.7369g of 2, 5-dihydroxyterephthalic acid (DHTA) were mixed and dissolved in a mixed solvent of 15mL of N, N-dimethylformamide DMF and 15mL of absolute ethanol, and the resulting mixture solution was sonicated for about 10 minutes to become a homogeneous solution, after which the solution was transferred to an autoclave lined with polytetrafluoroethylene and placed in an oven at 100℃for 24 hours. Then cooling the mixture to room temperature, centrifuging the mixture for 5min through 5000r/min, collecting a pale yellow product, washing the product with DMF and methanol for 2 times, and then drying the product in vacuum at 60 ℃ for 12h, thus obtaining Zn-MOF-74 yellow crystals through XRD verification.
Example 5:
in order to examine the effect of the solvent on the Zn-MOF-74 crystal material, the volume ratio of the solvent, namely N, N-dimethylformamide DMF, absolute ethyl alcohol and ultrapure water, was changed to be 3:1:1, and the reaction process is as follows: 3.2145g of zinc nitrate hexahydrate Zn (NO) 3 ) 2 ·6H 2 O and 0.7369g of 2, 5-dihydroxyterephthalic acid (DHTA) were mixed and dissolved in a mixed solvent of 18mL of N, N-dimethylformamide DMF, 6mL of absolute ethanol and 6mL of ultrapure water, and then the resulting mixture solution was sonicated for about 10 minutes to become a homogeneous solution, and then the solution was transferred to an autoclave lined with polytetrafluoroethylene and placed in an oven at 100℃for 24 hours. Then cooling the mixture to room temperature, centrifuging the mixture for 5min through 5000r/min, collecting a pale yellow product, washing the product with DMF and methanol for 4 times, and then drying the product in vacuum at 60 ℃ for 12h, thus obtaining Zn-MOF-74 yellow crystals through XRD verification.
Claims (14)
1. The application of Zn-MOF-74 metal organic framework material in toluene gas adsorption process is characterized in that: the preparation of the Zn-MOF-74 metal organic framework material comprises the following steps:
1) Zinc nitrate and 2, 5-dihydroxyterephthalic acid (DHTA) are dissolved in N, N-dimethylformamide DMF solvent or a mixed solvent of N, N-dimethylformamide DMF and absolute ethanol and/or water, and then the obtained mixture solution is treated into a homogeneous solution;
2) Transferring the solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, preserving heat for a certain time, cooling to room temperature, and centrifugally collecting a product;
3) Washed sequentially with DMF and methanol and then dried in vacuo to give Zn-MOF-74 material.
2. The use according to claim 1, characterized in that: the molar ratio of the zinc nitrate to the 2, 5-dihydroxyterephthalic acid (DHTA) in the step 1) is 1-4; the mass concentration of zinc nitrate in the solvent is 0.036-0.143 g/mL.
3. The use according to claim 1, characterized in that: the volume ratio of N, N-dimethylformamide DMF, absolute ethyl alcohol and water in the mixed solvent in the step 1) is 1-3:1-0:1-0.
4. The use according to claim 1, characterized in that: the step 1) of treating the homogeneous solution with the mixture solution refers to ultrasonic treatment, and the ultrasonic treatment time is 5-20min.
5. The use according to claim 1, characterized in that: and 2) heat preservation, namely, placing the materials into an oven for heat preservation, wherein the heat preservation temperature is 100-150 ℃ and the heat preservation time is 12-24h.
6. The use according to claim 1, characterized in that: the centrifugal rotating speed in the step 2) is 2000-8000r/min, and the centrifugal time is 5-10min.
7. The use according to claim 1, characterized in that: the washing times with DMF and methanol in the step 3) are 3-6 times;
the temperature of the vacuum drying in the step 3) is 60-80 ℃, and the drying time is 6-12h.
8. The use according to claim 2, characterized in that: the molar ratio of the zinc nitrate to the 2, 5-dihydroxyterephthalic acid (DHTA) in the step 1) is 2-3; the mass concentration of the zinc nitrate in the solvent is 0.072-0.107 g/mL.
9. A use according to claim 3, characterized in that: the volume ratio of the N, N-dimethylformamide DMF, the absolute ethyl alcohol and the water in the mixed solvent in the step 1) is 1:1:1-1:1:0.
10. The use according to claim 4, characterized in that: the step 1) of treating the homogeneous solution with the mixture solution refers to ultrasonic treatment, and the ultrasonic treatment time is 10-15 min.
11. The use according to claim 5, characterized in that: and 2) heat preservation, namely, placing the materials into an oven for heat preservation, wherein the heat preservation temperature is 100-130 ℃, and the heat preservation time is 18-24 h.
12. The use according to claim 6, characterized in that: the centrifugal rotating speed in the step 2) is 5000-8000 r/min, and the centrifugal time is 5-8 min.
13. The use according to claim 7, characterized in that: the washing times with DMF and methanol in the step 3) are 4-6 times;
the temperature of the vacuum drying in the step 3) is 60-70 ℃ and the drying time is 8-12 h.
14. The use according to claim 1, characterized in that: the application condition is normal temperature and normal pressure.
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Non-Patent Citations (4)
| Title |
|---|
| T. Grant Glover等.MOF-74 building unit has a direct impact on toxic gas adsorption.《CHEMICAL ENGINEERING SCIENCE》.2010,第66卷(第02期),第163-170页. * |
| 秦卫平.用于甲苯吸附的MOFs材料的合成及性能研究.《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2013,(第S2期),第B016-359页. * |
| 胡江亮等.CH4-N2在MOFs结构材料中的吸附分离性能.《化工学报》.2015,第66卷(第09期),第3518-3528页. * |
| 陈沭璇等.MOFs自牺牲模板法制备ZnO及其对NO2的气敏性能.《无机化学学报》.2020,第36卷(第09期),第1639-1648页. * |
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