CN115124676A - Preparation method and application of halogen modified covalent organic framework material - Google Patents
Preparation method and application of halogen modified covalent organic framework material Download PDFInfo
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title claims abstract description 46
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 16
- 150000002367 halogens Chemical class 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 34
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 19
- 238000000227 grinding Methods 0.000 claims abstract description 19
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 diamine salt Chemical class 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 10
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- KAPNIDMXEKQLMQ-UHFFFAOYSA-N 2,4,6-trihydroxybenzene-1,3,5-tricarbaldehyde Chemical compound OC1=C(C=O)C(O)=C(C=O)C(O)=C1C=O KAPNIDMXEKQLMQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- FXFTWEVIIHVHDS-UHFFFAOYSA-N 2-fluorobenzene-1,4-diamine Chemical compound NC1=CC=C(N)C(F)=C1 FXFTWEVIIHVHDS-UHFFFAOYSA-N 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- 238000000944 Soxhlet extraction Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- NGULVTOQNLILMZ-UHFFFAOYSA-N 2-bromobenzene-1,4-diamine Chemical compound NC1=CC=C(N)C(Br)=C1 NGULVTOQNLILMZ-UHFFFAOYSA-N 0.000 claims description 2
- MGLZGLAFFOMWPB-UHFFFAOYSA-N 2-chloro-1,4-phenylenediamine Chemical compound NC1=CC=C(N)C(Cl)=C1 MGLZGLAFFOMWPB-UHFFFAOYSA-N 0.000 claims description 2
- CAAOWHHLKPUWHW-UHFFFAOYSA-N 2-iodobenzene-1,4-diamine Chemical compound NC1=CC=C(N)C(I)=C1 CAAOWHHLKPUWHW-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 25
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000005120 petroleum cracking Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000002955 isolation Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 11
- 239000012621 metal-organic framework Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000004729 solvothermal method Methods 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- MHXLAKJJNRIVDR-UHFFFAOYSA-N 2,4,6-trihydroxybenzene-1,3,5-tricarboxylic acid Chemical compound OC1=C(C(=C(C(=C1C(=O)O)O)C(=O)O)O)C(=O)O MHXLAKJJNRIVDR-UHFFFAOYSA-N 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005388 cross polarization Methods 0.000 description 1
- 238000005384 cross polarization magic-angle spinning Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- 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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
- C08G12/08—Amines aromatic
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
- B01D2253/204—Metal organic frameworks (MOF's)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7022—Aliphatic hydrocarbons
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Abstract
The invention provides a method for efficiently preparing a halogen modified covalent organic framework material by using a grinding method and application thereof, belonging to the technical field of new material preparation and gas adsorption separation. Firstly, reacting halogen-containing p-phenylenediamine with p-toluenesulfonic acid to obtain diamine salt, and then reacting with 2,4, 6-trihydroxy-1, 3, 5-benzene triformal by a grinding method to prepare the halogen modified covalent organic framework material. The method has the advantages of simple process, short synthesis period, no need of air isolation, economy, environmental protection and expanded production. The material shows good acetylene adsorption separation selectivity and has high application potential in the fields of petroleum cracking and acetylene production.
Description
Technical Field
The invention belongs to the technical field of preparation of new materials and gas adsorption separation, and particularly relates to a method for preparing a halogen modified covalent organic framework material by using a grinding method and application thereof.
Background
Covalent organic framework materials (COFs) have the characteristics of high specific surface area, easily-regulated structure, uniform pore diameter, rich active adsorption sites, good chemical stability and thermal stability and the like, and are widely applied to the fields of heterogeneous catalysis, gas separation, electric energy storage and the like. In recent years, because the structure of the COFs has high controllability, the COFs becomes one of hot spot materials in the aspects of gas capture and separation, and the functional modification of the COFs framework by using different substituent groups is a main method for regulating the structure of the COFs. The halogen has stronger electronegativity, is a functional group with wide application, has the effects of stabilizing chemical properties, adjusting charges, anchoring guest molecules or providing substitution sites, adjusting hydrophobicity and the like, can be used for adjusting the electronic structure and the pore size of COFs, and realizes efficient adsorption and separation of gases.
At present, metal organic framework Materials (MOFs) containing high-activity metal adsorption sites are porous nanomaterials with excellent acetylene selectivity and adsorption capacity. However, because of the defects of easy hydrolysis, insufficient stability and the like of MOFs, the application of MOFs in industrial production conditions of petroleum cracking, acetylene preparation and the like still has great difficulty. Compared with MOFs, COFs are composed of light elements such as light element C, N, O, H, B, do not contain heavy metal elements, are connected through strong covalent bonds in a framework structure, and have higher stability. In addition, the structure and the pores can be orderly regulated and controlled, and the functional groups are introduced to synthesize and modify the functional groups according to target requirements. However, the traditional solvothermal synthesis method of COFs has the defects of harsh preparation conditions (air isolation), low synthesis efficiency (long period), poor repeatability and the like, so that the application of COFs materials in the field of acetylene adsorption separation is less. Therefore, the method for synthesizing the COFs by multiple strategies is simple in process, short in synthesis period, economical and environment-friendly, and capable of performing large-scale expanded production, and is an effective way for applying the COFs to the industrial field.
The COFs are synthesized by a solvothermal method, wherein different precursors and required solvents are added into a reaction container, a reaction system is converted into a vacuum environment, and then reaction is carried out at a certain temperature and pressure, so that the required COFs are finally obtained. The method has harsh experimental conditions, needs to ensure the vacuum environment of a reaction system, has a long reaction period of 72 hours generally, and needs to regulate and control the solvent ratio, so that the experimental result has poor repeatability, and the final synthesis efficiency is greatly influenced. In contrast, the COFs synthesized by mechanical grinding method can not only mix the precursors fully and uniformly, but also does not need to use a large amount of solvent. Therefore, the grinding method has the advantages of simple operation, economy, environmental protection, short reaction period and the like, and provides a new idea and a new method for the synthesis of COFs.
The halogen atom modified COFs synthesized by the grinding method has good adsorption selectivity and adsorption capacity for acetylene, and provides an important preparation idea for industrial application of the COFs in the acetylene adsorption field.
Disclosure of Invention
The invention aims to provide a novel halogen-containing covalent organic framework material.
Another object of the present invention is to provide a simple, fast, economical and environment-friendly preparation method of the covalent organic framework material.
It is also an object of the present invention to provide gas adsorption applications of the covalent organic framework materials.
On one hand, the invention provides a grinding preparation method of a covalent organic framework gas adsorption material, which is characterized by comprising the following steps of: the method comprises the following steps:
(1) reacting halogen-containing p-phenylenediamine with p-toluenesulfonic acid to form diamine salt crystals;
(2) uniformly mixing diamine salt crystals and 2,4, 6-trihydroxy-1, 3, 5-benzene triformal, grinding, dropwise adding a trace amount of deionized water in the grinding process to obtain a paste, and heating at 80-100 ℃ to obtain red powder;
(3) and after the reaction is finished, washing the product by a Soxhlet extraction method, and then drying in vacuum to obtain the halogen atom modified covalent organic framework material.
In a preferred technical embodiment, the halogen-containing p-phenylenediamine is one of 2-fluoro-1, 4-phenylenediamine, 2-chloro-1, 4-phenylenediamine, 2-bromo-1, 4-phenylenediamine and 2-iodo-1, 4-phenylenediamine.
In a preferred technical embodiment, the 2,4, 6-trihydroxy-1, 3, 5-benzene tricarboaldehyde in the step (2) is 63mg to 1000mg, and the molar ratio of the 2,4, 6-trihydroxy-1, 3, 5-benzene tricarboaldehyde to the halogen-containing p-phenylenediamine and the p-toluenesulfonic acid is 1: 1.5: 5-10; the proportion of the 2,4, 6-trihydroxy-1, 3, 5-benzene tricarboaldehyde to the dropwise added deionized water is 63 mg: 50-100 μ L.
In a preferable technical embodiment, the grinding time in the step (2) is 20-30 min, and after the liquid is added, the grinding is continued for 10-20 min.
In a preferred technical embodiment, the solvent used for washing in step (3) is deionized water, N-dimethylformamide, acetone and methanol, and the number of washing times is 3-5.
In a preferred technical embodiment, the vacuum drying in the step (3) has the process parameters of drying temperature of 100-150 ℃ and time of 12-48 h.
In another aspect, the present invention provides a covalent organic framework material (designated TpPa-F) synthesized by reacting 2-fluoro-1, 4-phenylenediamine with p-toluenesulfonic acid to form diamine salt crystals, followed by milling with 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic acid.
In yet another aspect, the covalent organic framework materials of the present invention are used for adsorptive separation of acetylene gas.
The preparation and application of the covalent organic framework material TpPa-F for gas adsorption provided by the invention have the following advantages:
(1) the invention utilizes COFs prepared by a grinding method, has simple and rapid synthesis method, and has short synthesis period compared with a solvothermal method, does not need to add any organic solvent, and is economic and environment-friendly.
(2) The COFs prepared by the method is mainly used for adsorbing acetylene gas, and active sites for adsorbing acetylene are increased by introducing halogen atoms into the COFs, so that the selectivity and the adsorption quantity of acetylene are enhanced.
(3) The COFs prepared by the method has higher stability, provides a new material for the industrial application of the adsorption separation of acetylene gas, and has higher application potential in the fields of petroleum cracking and acetylene production.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic diagram of the synthesis of a covalent organic framework material of the present invention;
FIG. 2 is an XRD spectrum of a covalent organic framework material of the present invention;
FIG. 3 is an SEM image of a covalent organic framework material of the present invention;
FIG. 4 is a solid NMR spectrum of a covalent organic framework material of the invention;
FIG. 5 is N of a covalent organic framework material of the invention 2 Adsorption-desorption curve chart and aperture distribution curve;
FIG. 6 is a graph of acetylene adsorption for a covalent organic framework material of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples.
Example 1: preparation of covalent organic framework material TpPa-F of the invention
This example is the preparation of covalent organic framework material TpPa-F, as shown in fig. 1, the specific preparation method is:
reacting 2-fluoro-1, 4-phenylenediamine with p-toluenesulfonic acid to form diamine salt crystals; grinding the diamine salt crystals for 20min, adding 2,4, 6-trihydroxy-1, 3, 5-benzene tricarboxaldehyde, grinding for 20min, dripping 100 mu L of deionized water in the grinding process to obtain a paste, and heating at 90 ℃ to obtain red powder; after the reaction is finished, the product is washed by deionized water, N-dimethylformamide, acetone and methanol by a Soxhlet extraction method, and then is put into a vacuum oven to be dried for 24 hours in vacuum at 120 ℃ to obtain the covalent organic framework material TpPa-F modified by fluorine atoms.
Example 2: structural characterization of covalent organic framework material TpPa-F of the invention
The present example is a structural characterization of a covalent organic framework material TpPa-F, specifically as follows:
XRD spectrum
The X-ray diffraction (XRD) pattern of the covalent organic framework material TpPa-F is shown in FIG. 2, the scanning range is from 3 degrees to 40 degrees, and the scanning speed is 5 degrees min -1 Covalent organic framework materials TpPa-F has diffraction characteristic peaks at 2 theta of 4.68 degrees, 8.06 degrees, 9.30 degrees, 12.30 degrees and 26.50 degrees, and is basically similar to literature reports, thereby indicating that the TpPa-F is successfully synthesized.
SEM image
Analyzing the morphology structure of the covalent organic framework material TpPa-F by adopting a scanning electron microscope: as can be seen from fig. 3, the covalent organic framework material TpPa-F exhibits a bulk structure of clusters.
3. Nuclear magnetic resonance spectrum of solid
Of covalent organic framework materials TpPa-F 13 The C cross-polarization magic angle rotation (CP/MAS) nuclear magnetic resonance spectrum is shown in fig. 4, further confirming the presence of C ═ N, indicating successful synthesis of covalent organic framework material TpPa-F.
Example 3: gas adsorption performance test of covalent organic framework material TpPa-F
1.N 2 Adsorption-desorption curve chart and aperture distribution curve
And measuring the specific surface area and the pore volume of the covalent organic framework material TpPa-F by using a nitrogen adsorption BET specific surface area measuring instrument. The measured result is as follows: the specific surface area of the covalent organic framework material TpPa-F is 1048 (m) 3 g -1 ) Pore size of
N thereof 2 The adsorption-desorption curve is shown in fig. 4, demonstrating the microporous structure of the material.
2. Acetylene adsorption curve
The adsorption curve of covalent organic framework material TpPa-F on acetylene is shown in FIG. 6, and the adsorption curve is related to CO 2 Compared with the prior art, the adsorption capacity of the TpPa-F to acetylene is obviously increased at two different temperatures of 273K and 298K, which shows that the TpPa-F has good adsorption selectivity and adsorption capacity to acetylene.
Claims (7)
1. A preparation method of a halogen modified covalent organic framework material is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) reacting halogen-containing p-phenylenediamine with p-toluenesulfonic acid to form diamine salt crystals;
(2) uniformly mixing diamine salt crystals and 2,4, 6-trihydroxy-1, 3, 5-benzene triformol, grinding, dropwise adding a trace amount of deionized water in the grinding process to obtain a muddy substance, and heating at 80-100 ℃ to obtain red powder;
(3) after the reaction is finished, washing the product by a Soxhlet extraction method, and then drying in vacuum to obtain the covalent organic framework material modified by the halogen atom.
2. The method according to claim 1, wherein the halogen-containing p-phenylenediamine is one of 2-fluoro-1, 4-phenylenediamine, 2-chloro-1, 4-phenylenediamine, 2-bromo-1, 4-phenylenediamine, and 2-iodo-1, 4-phenylenediamine.
3. The method according to claim 1, wherein the 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic aldehyde in the step (2) is 63mg to 1000mg, and the molar ratio of the 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic aldehyde to the halogen-containing p-phenylenediamine and the p-toluenesulfonic acid is 1: 1.5: 5-10; the proportion of the 2,4, 6-trihydroxy-1, 3, 5-benzene tricarboaldehyde to the dropwise added deionized water is 63 mg: 50-100 μ L.
4. The method according to claim 1, wherein the grinding time in the step (2) is 20-30 min, and after the liquid is added, the grinding is continued for 10-20 min.
5. The method according to claim 1, wherein the solvent used for washing in step (3) is deionized water, N-dimethylformamide, acetone and methanol, and the number of washing times is 3 to 5.
6. The method according to claim 1, wherein the process parameters of the vacuum drying in the step (3) are as follows: the drying temperature is 100-150 ℃, and the drying time is 12-48 h.
7. Use of a covalent organic framework material containing halogen based on any of claims 1-2 for the capture and separation of acetylene gas.
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