CN115124675B - Two-dimensional diamond-shaped hetero-pore covalent organic framework material and preparation method thereof - Google Patents
Two-dimensional diamond-shaped hetero-pore covalent organic framework material and preparation method thereof Download PDFInfo
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 78
- 239000000463 material Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011148 porous material Substances 0.000 title claims abstract description 17
- PAYGAVVJLIFANV-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarbaldehyde Chemical class O=CC1=C(C=O)C(C=O)=CC(C=2C=CC=CC=2)=C1C=O PAYGAVVJLIFANV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical class C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002262 Schiff base Substances 0.000 claims abstract description 4
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 4
- 238000010276 construction Methods 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 229910003460 diamond Inorganic materials 0.000 claims description 29
- 239000010432 diamond Substances 0.000 claims description 29
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 15
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 14
- 239000007810 chemical reaction solvent Substances 0.000 claims description 14
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 14
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 7
- 238000000944 Soxhlet extraction Methods 0.000 claims description 7
- KSZVHVUMUSIKTC-UHFFFAOYSA-N acetic acid;propan-2-one Chemical compound CC(C)=O.CC(O)=O KSZVHVUMUSIKTC-UHFFFAOYSA-N 0.000 claims description 6
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 3
- 239000013384 organic framework Substances 0.000 claims description 3
- KSSJBGNOJJETTC-UHFFFAOYSA-N COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC Chemical class COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC KSSJBGNOJJETTC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 238000010586 diagram Methods 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 6
- 239000013475 COF-5 Substances 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- 239000013474 COF-1 Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- -1 tetraphenylethylene tetramine Chemical compound 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- HCCZWCVYJTUDJY-UHFFFAOYSA-N pyrene-1,2,3,4-tetramine Chemical class C1=CC=C2C=C(N)C3=C(N)C(N)=C(N)C4=CC=C1C2=C43 HCCZWCVYJTUDJY-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a two-dimensional diamond-shaped hetero-pore covalent organic framework material and a preparation method thereof, and belongs to the field of covalent organic framework materials. The material consists of C with an included angle of 60 DEG and an included angle of 120 DEG 2v The symmetrical construction unit biphenyl tetra-aldehyde derivative and the tetramine derivative with an included angle of 120 degrees and an included angle of 60 degrees are obtained through Schiff base reaction, and a new design idea is provided for the two-dimensional special-shaped hole covalent organic framework material. The material has a stable skeleton structure, and has the advantages of high specific surface area, good mass transportation, widely distributed active sites, minimized diffusion barrier and the like.
Description
Technical Field
The invention belongs to the field of covalent organic framework materials, and particularly relates to a two-dimensional diamond-shaped hetero-pore covalent organic framework material and a preparation method thereof.
Technical Field
Two-dimensional (2D) Covalent Organic Frameworks (COFs) are generally planar network structures formed by rigid building blocks linked by covalent bonds. Pore engineering of two-dimensional COFs is focused mainly on the topology of the framework, which includes engineering of the shape, size and distribution of pores, which can be designed by combining building blocks of different sizes and specific symmetries. The pore size and shape in COFs can be precisely controlled by the symmetry and length of the building block. Since the first COF was developed in Yaghi 2005, COFs with 58 different pores of tetragonal, hexagonal, and triangular shapes have been designed and synthesized.
In the related art, most of the COF frameworks generally exhibit uniform porosity, which is called single pore COF, and thus it is still challenging to introduce different types of pores into the same covalent organic framework and maintain a stable configuration.
Disclosure of Invention
In order to overcome the defects in the related art, the invention aims to provide a two-dimensional diamond-shaped heterogeneous covalent organic framework material and a preparation method thereof. According to the method, a series of biphenyl tetra-aldehyde derivatives are designed and synthesized, and the biphenyl tetra-aldehyde derivatives and tetramine derivative building units are subjected to solvothermal reaction to obtain the two-dimensional diamond hetero-pore covalent organic framework material which has a stable framework structure, so that a new design idea is provided for the two-dimensional hetero-pore covalent organic framework material.
In order to achieve the above purpose, the invention adopts the following technical scheme:
as a first aspect of the present invention, there is provided a two-dimensional diamond shaped hetero-porous covalent organic framework material consisting of C having an included angle of 60 ° and an included angle of 120 ° 2v The symmetrical construction unit biphenyl tetra-aldehyde derivative and the tetramine derivative with an included angle of 120 degrees and an included angle of 60 degrees form a covalent organic framework material with at least two-dimensional diamond-shaped hetero holes through Schiff base reaction.
Optionally, the organic framework material has the following structure:
as a second aspect of the present invention, a preparation method of a two-dimensional diamond-shaped heterogeneous covalent organic framework material is provided, in which biphenyl tetra-aldehyde derivatives and tetra-amine derivatives are used as raw materials and dissolved in a reaction solvent, the reaction is performed under the action of a catalyst, after the reaction is finished, the procedure is cooled to room temperature, and the solid is filtered, washed and collected, so as to obtain the two-dimensional diamond-shaped heterogeneous covalent organic framework material; the biphenyl tetra-aldehyde derivative has any one of the following structures:
the tetramine derivative has any one of the following structures:
optionally, the mass ratio of the biphenyl tetra-aldehyde derivative to the tetramine derivative is 1:1. Alternatively, the reaction solvent is a mixture of mesitylene and o-dichlorobenzene, or a mixture of o-dichlorobenzene and n-butanol, or a mixture of mesitylene and 1, 4-dioxane.
The volume ratio of the mesitylene to the o-dichlorobenzene is 1:5-1:1, the volume ratio of the o-dichlorobenzene to the n-butanol is 1:5-1:1, and the volume ratio of the mesitylene to the 1, 4-dioxane is 1:5-1:1.
Optionally, the catalyst is acetic acid, and the concentration of the acetic acid is 3-6 mol/L; the catalyst is used in an amount of 10-20% by volume of the reaction solvent.
Alternatively, the conditions of the reaction are: standing for 3-7 days at 100-150 ℃.
Optionally, after the collecting the solid, further comprises a purification and drying step, wherein the drying conditions are as follows: vacuum, 60-120 ℃; the purification mode adopts Soxhlet extraction.
Optionally, the organic solvent used for washing comprises at least one of N, N-dimethylformamide DMF, tetrahydrofuran THF and Acetone acetate.
The invention has at least the following beneficial effects:
the invention constructs a covalent organic framework material with at least two-dimensional diamond-shaped hetero-pores by using biphenyl tetra-aldehyde derivatives and tetramine derivatives. According to the preparation method provided by the invention, the two-dimensional diamond heteropore covalent organic framework based on the biphenyl tetra-aldehyde derivative framework can be prepared, and has a stable framework structure, and functional groups and proper pore canal structures allow the covalent organic framework to accurately capture guest molecules. The material with the heteroporous structure has the advantages of high specific surface area, good mass transportation, wide distribution of active sites, minimized diffusion barrier and the like.
Drawings
The invention is further described below with reference to the accompanying drawings:
FIG. 1 is a schematic diagram of a synthetic route for two-dimensional diamond-shaped heterogeneous covalent organic framework materials RH-COF-1 and RH-COF-2, provided in an exemplary embodiment of the present invention, wherein when R is all H, it is denoted RH-COF-1; when R is all OH, it is denoted RH-COF-2;
FIG. 2 is a schematic diagram of a synthetic route for two-dimensional diamond-shaped heterogeneous covalent organic framework materials RH-COF-3 and RH-COF-4, wherein when R is all H, it is denoted as RH-COF-3, according to an exemplary embodiment of the present invention; when R is all OH, it is designated RH-COF-4.
FIG. 3 is a schematic diagram of a synthetic route for two-dimensional diamond-shaped heterogeneous covalent organic framework materials RH-COF-5 and RH-COF-6, according to an exemplary embodiment of the present invention, wherein when R is all H, it is denoted RH-COF-5; when R is all OH, it is designated RH-COF-6.
FIG. 4 is a schematic diagram of a synthetic route for two-dimensional diamond-shaped heterogeneous covalent organic framework materials RH-COF-7 and RH-COF-8, according to an exemplary embodiment of the present invention, wherein when R is all H, it is denoted RH-COF-7; when R is all OH, it is designated RH-COF-8.
FIG. 5 is a schematic diagram of a synthetic route for two-dimensional diamond-shaped heterogeneous covalent organic framework materials RH-COF-9 and RH-COF-10, according to an exemplary embodiment of the present invention, wherein when R is all H, it is denoted RH-COF-9; when R is all OH, it is designated RH-COF-10.
FIG. 6 is a schematic diagram of a synthetic route for two-dimensional diamond-shaped heterogeneous covalent organic framework materials RH-COF-11 and RH-COF-12, according to an exemplary embodiment of the present invention, wherein when R is all H, it is denoted RH-COF-11; when R is all OH, it is designated RH-COF-12.
FIG. 7 is a schematic diagram of a synthetic route for two-dimensional diamond-shaped heterogeneous covalent organic framework materials RH-COF-13, RH-COF-14, RH-COF-15 and RH-COF-16, according to an exemplary embodiment of the present invention, wherein when R is all H and X is all H, the two-dimensional diamond-shaped heterogeneous covalent organic framework materials are denoted as RH-COF-13; when R is all OH and X is all H, the R is RH-COF-14; when R is all H, X is all CH 3 When it is, it is designated RH-COF-15; when R is all OH and X is all CH 3 And is designated RH-COF-16.
FIG. 8 is a schematic diagram of a synthetic route for two-dimensional diamond-shaped heterogeneous covalent organic framework materials RH-COF-17 and RH-COF-18, according to an exemplary embodiment of the present invention, wherein when R is all H, it is denoted RH-COF-17; when R is all OH, it is designated RH-COF-18.
FIG. 9 is an infrared spectrum of two-dimensional diamond-shaped heterogeneous covalent organic framework materials RH-COF-2 and HP-COF-4 provided in an exemplary embodiment of the present invention;
FIG. 10 is an infrared spectrum of two-dimensional diamond-shaped heterogeneous covalent organic framework materials RH-COF-8, RH-COF-10 provided by an exemplary embodiment of the present invention;
FIG. 11 is an infrared spectrum of two-dimensional heterogeneous covalent organic framework materials RH-COF-12 and RH-COF-14 according to an exemplary embodiment of the present invention.
FIG. 12 is a two-dimensional diamond-shaped heterogeneous covalent organic framework material RH-COF-2N provided in an exemplary embodiment of the invention 2 Desorption profile.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to specific embodiments.
The two-dimensional diamond hetero-pore covalent organic framework material of the specific embodiment of the invention is formed by C with an included angle of 60 degrees and an included angle of 120 degrees 2v The symmetrical construction unit biphenyl tetra-aldehyde derivative and the tetramine derivative with an included angle of 120 degrees and an included angle of 60 degrees form the covalent organic framework material with at least two-dimensional diamond-shaped different holes through Schiff base reaction.
The two-dimensional diamond-shaped hetero-pore covalent organic framework material of the specific embodiment of the invention has the following structure:
the preparation method of the two-dimensional diamond heterogeneous covalent organic framework material comprises the following steps of: dissolving biphenyl tetra-aldehyde derivatives and tetramine derivatives serving as raw materials in a reaction solvent, reacting under the action of a catalyst, cooling to room temperature after the reaction is finished, filtering, washing and collecting solids to obtain the two-dimensional diamond heterogeneous covalent organic framework material;
the biphenyl tetra-aldehyde derivative has any one of the following structures:
the tetramine derivative has any one of the following structures:
the preparation method of the two-dimensional diamond heterogeneous covalent organic framework material comprises the following steps of: 1. by adopting the proportion, the two-dimensional diamond heterogeneous covalent organic framework material with stable structure can be obtained.
The preparation method of the two-dimensional diamond-shaped heterogeneous covalent organic framework material comprises the step of preparing a reaction solvent, wherein the reaction solvent is a mixture of mesitylene and o-dichlorobenzene, or a mixture of o-dichlorobenzene and n-butanol, or a mixture of mesitylene and 1, 4-dioxane. The organic framework material has two ligands, only one ligand can be dissolved in a single solvent, and the two solvents are beneficial to improving the solubility of the monomer.
The preparation method of the two-dimensional diamond heterogeneous covalent organic framework material comprises the following steps of: 5 to 1:1, the volume ratio of the o-dichlorobenzene to the n-butanol is 1:5 to 1:1, wherein the volume ratio of the mesitylene to the 1, 4-dioxane is 1:5 to 1:1. different raw material proportions have great influence on the crystallinity of the material, and the proper proportion is favorable for obtaining the best crystallinity.
The preparation method of the two-dimensional diamond heterogeneous covalent organic framework material comprises the steps that the catalyst is acetic acid, and the concentration of the acetic acid is 3-6 mol/L; the catalyst is used in an amount of 10-20% by volume of the reaction solvent. Acetic acid is used in the above concentration range, which is advantageous in controlling the reaction rate.
The preparation method of the two-dimensional diamond heteropore covalent organic framework in the specific embodiment of the invention comprises the following reaction conditions: standing for 3-7 days at 100-150 ℃.
The preparation method of the two-dimensional diamond heterogeneous covalent organic framework material in the specific embodiment of the invention further comprises the steps of purification and drying after the solid is collected, wherein the drying conditions are as follows: vacuum, 60-120 ℃; the purification mode adopts Soxhlet extraction.
According to the preparation method of the two-dimensional diamond-shaped heterogeneous covalent organic framework material, the organic solvent adopted in the washing comprises at least one of N, N-dimethylformamide DMF, tetrahydrofuran THF and Acetone acetate, and the organic solvent adopted in the washing can be N, N-dimethylformamide DMF, tetrahydrofuran THF or Acetone acetate, or can be a mixture of N, N-dimethylformamide DMF and tetrahydrofuran THF, a mixture of tetrahydrofuran THF and Acetone acetate or a mixture of N, N-dimethylformamide DMF and Acetone acetate, or the like.
Example 1
The two-dimensional diamond heterogeneous covalent organic framework materials RH-COF-1, RH-COF-2, RH-COF-3 and RH-COF-4 provided by the embodiment are obtained by the following preparation methods:
(1) 3,3', 5' -tetra-aldehyde-4, 4' -dihydroxybiphenyl and 3,3', 5' -tetra-aldehyde biphenyl are designed and synthesized.
(2) 0.0268mmol of biphenyl tetra-aldehyde derivative and 0.0268mmol of pyrenetetramine derivative (synthetic schematic diagrams are shown in fig. 1 and 2) are added into a mixed reaction solvent of 0.5mL of mesitylene and 1.5mL of o-dichlorobenzene, and the mixture is uniformly dispersed by ultrasonic.
(3) Adding 0.2mL of 6mol/L acetic acid serving as a catalyst into the uniformly dispersed solution, and adding the solution into a glass tube after ultrasonic dispersion is uniform.
(4) The glass tube is kept stand for 3 days at a constant temperature in a 120 ℃ oven, and after the reaction is finished, the temperature is reduced to room temperature by a program, and the solid is collected by filtration.
(5) The collected solids were washed 6ml×5 times with DMF followed by THF centrifugation and the solids were collected again.
(6) The solid is soaked in DMF until the solution is colorless, and then is subjected to Soxhlet extraction in THF for 24 hours, and then is subjected to vacuum drying at 90 ℃ for 8 hours to obtain brick red powder, namely the two-dimensional diamond heterogeneous covalent organic framework material, which is marked as RH-COF-1, RH-COF-2, RH-COF-3 and RH-COF-4.
The infrared spectrograms of the two-dimensional diamond heterogeneous covalent organic framework materials RH-COF-2 and RH-COF-4 obtained in the embodiment are shown in FIG. 9, and C=N bonds are generated, so that successful synthesis of the products is proved. Referring to FIG. 12, a two-dimensional diamond-shaped heterogeneous covalent organic framework material RH-COF-2N prepared in this example 2 It can be seen that it has a higher specific surface area. Other two-dimensional diamond-shaped heterogeneous covalent organic framework materials in the specific embodiment of the invention are all higher in specific surface area through verification by the characterization method, and part of the materials are not shown.
Example 2
The two-dimensional diamond heterogeneous covalent organic framework materials RH-COF-7, RH-COF-8, RH-COF-9 and RH-COF-10 provided by the embodiment are obtained by the following preparation methods:
(1) 3,3', 5' -tetra-aldehyde-4, 4' -dihydroxybiphenyl and 3,3', 5' -tetra-aldehyde biphenyl are designed and synthesized.
(2) 0.02mmol of biphenyl tetra-aldehyde derivative and 0.02mmol of tetraphenylethylene tetramine (synthetic schematic diagrams are shown in fig. 4 and 5) are added into 1.0mL of mixed reaction solvent of mesitylene and 1.0mL of o-dichlorobenzene, and the mixture is uniformly dispersed by ultrasonic.
(3) Adding 0.2mL of 6mol/L acetic acid serving as a catalyst into the uniformly dispersed solution, and adding the solution into a glass tube after ultrasonic dispersion is uniform.
(4) The glass tube is kept stand for 3 days at a constant temperature in a 120 ℃ oven, and after the reaction is finished, the temperature is reduced to room temperature by a program, and the solid is collected by filtration.
(5) The collected solids were washed 8ml×5 times with DMF followed by THF centrifugation and the solids were collected again.
(6) The solid is soaked in DMF until the solution is colorless, and then after Soxhlet extraction is carried out in THF for 24 hours, the powder is dried in vacuum at 90 ℃ for 8 hours to obtain reddish brown powder, namely the two-dimensional diamond heterogeneous covalent organic framework material, which is marked as RH-COF-7, RH-COF-8, RH-COF-9 and RH-COF-10.
The infrared spectrograms of the two-dimensional diamond heterogeneous covalent organic framework materials RH-COF-8 and RH-COF-10 obtained in the embodiment are shown in FIG. 10, and C=N bonds are generated, so that successful synthesis of the products is proved.
Example 3
The two-dimensional diamond heterogeneous covalent organic framework materials RH-COF-11, RH-COF-12, RH-COF-13, RH-COF-14, RH-COF-15 and RH-COF-16 provided by the embodiment are obtained by the following preparation methods:
(1) 3,3', 5' -tetra-aldehyde-4, 4' -dihydroxybiphenyl and 3,3', 5' -tetra-aldehyde biphenyl are designed and synthesized.
(2) 0.03mmol of biphenyl tetra-aldehyde derivative and 0.03mmol of benzene tetra-amine derivative (synthetic schematic diagrams are shown in fig. 6 and 7) are added into a mixed reaction solvent of 1.0mL of o-dichlorobenzene and 1.0mL of n-butanol, and ultrasonic dispersion is uniform.
(3) Adding 0.2mL of 3mol/L acetic acid serving as a catalyst into the uniformly dispersed solution, and adding the solution into a glass tube after ultrasonic dispersion is uniform.
(4) The glass tube is kept stand for 5 days at a constant temperature in a 120 ℃ oven, and after the reaction is finished, the temperature is reduced to room temperature by a program, and the solid is collected by filtration.
(5) The collected solids were washed 6ml×5 times with DMF followed by THF centrifugation and the solids were collected again.
(6) The solid is soaked in DMF until the solution is colorless, and then after Soxhlet extraction is carried out in THF for 24 hours, the powder is dried in vacuum at 90 ℃ for 10 hours to obtain reddish brown powder, namely the two-dimensional diamond heterogeneous covalent organic framework material, which is marked as RH-COF-11, RH-COF-12, RH-COF-13, RH-COF-14, RH-COF-15 and RH-COF-16.
The infrared spectrograms of the two-dimensional diamond heterogeneous covalent organic framework materials RH-COF-12 and RH-COF-14 obtained in the embodiment are shown in FIG. 11, and C=N bonds are generated, so that successful synthesis of the products is proved.
Example 4
The two-dimensional diamond heterogeneous covalent organic framework materials RH-COF-5, RH-COF-6, RH-COF-17 and RH-COF-18 provided by the embodiment are obtained by the following preparation methods:
(1) 3,3', 5' -tetra-aldehyde-4, 4' -dihydroxybiphenyl and 3,3', 5' -tetra-aldehyde biphenyl are designed and synthesized.
(2) 0.0268mmol of biphenyl tetra-aldehyde derivative and 0.0268mmol of tetramine derivative (synthetic schematic diagrams are shown in fig. 3 and 8) are added into a mixed reaction solvent of 0.4mL of mesitylene and 1.6mL of 1, 4-dioxane, and the mixture is uniformly dispersed by ultrasonic.
(3) Adding 0.3mL of 3mol/L acetic acid serving as a catalyst into the uniformly dispersed solution, and adding the solution into a glass tube after ultrasonic dispersion is uniform.
(4) The glass tube was allowed to stand at constant temperature in an oven at 100℃for 7 days, cooled to room temperature after the reaction was completed and the solid was collected by filtration.
(5) The collected solids were washed 10ml×6 times with DMF followed by THF centrifugation and the solids were collected again.
(6) And (3) soaking the solid in DMF until the solution is colorless, performing Soxhlet extraction in THF for 24 hours, and then performing vacuum drying at 120 ℃ for 8 hours to obtain reddish brown powder, namely the two-dimensional diamond heterogeneous covalent organic framework materials RH-COF-5, RH-COF-6, RH-COF-17 and RH-COF-18.
It can be understood that the two-dimensional diamond-shaped heterogeneous covalent organic framework materials RH-COF-5, RH-COF-6, RH-COF-17 and RH-COF-18 obtained in this embodiment can be characterized by the infrared spectroscopy, so that successful synthesis of the products is proved, and details are omitted here.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention.
Claims (10)
1. A two-dimensional diamond hetero-pore covalent organic framework material, which is characterized by comprising C with an included angle of 60 DEG and an included angle of 120 DEG 2v The symmetrical construction unit biphenyl tetra-aldehyde derivative and tetramine derivative with 120-degree included angle and 60-degree included angle are formed into the product through Schiff base reactionAt least two-dimensional diamond shaped heteroaperture covalent organic framework materials.
2. The two-dimensional diamond shaped heterogeneous covalent organic framework material of claim 1, wherein the organic framework material has the following structure:
3. a method of preparing a two-dimensional diamond shaped heterogeneous covalent organic framework material according to claim 1, comprising the steps of: dissolving biphenyl tetra-aldehyde derivatives and tetramine derivatives serving as raw materials in a reaction solvent, reacting under the action of a catalyst, cooling to room temperature after the reaction is finished, filtering, washing and collecting solids to obtain the two-dimensional diamond heterogeneous covalent organic framework material;
the biphenyl tetra-aldehyde derivative has any one of the following structures:
the tetramine derivative has any one of the following structures:
4. the method for preparing a two-dimensional diamond-shaped heterogeneous covalent organic framework material according to claim 3, wherein the mass ratio of the biphenyl tetra-aldehyde derivative to the tetra-amine derivative is 1:1.
5. The method for preparing a two-dimensional diamond-shaped heterogeneous covalent organic framework material according to claim 3, wherein the reaction solvent is a mixture of mesitylene and o-dichlorobenzene, or a mixture of o-dichlorobenzene and n-butanol, or a mixture of mesitylene and 1, 4-dioxane.
6. The preparation method of the two-dimensional diamond-shaped heterogeneous covalent organic framework material according to claim 5, wherein the volume ratio of mesitylene to o-dichlorobenzene is 1:5-1:1, the volume ratio of o-dichlorobenzene to n-butanol is 1:5-1:1, and the volume ratio of mesitylene to 1, 4-dioxane is 1:5-1:1.
7. The method for preparing the two-dimensional diamond-shaped heterogeneous covalent organic framework material according to claim 5, wherein the catalyst is acetic acid, and the concentration of the acetic acid is 3-6 mol/L; the catalyst is used in an amount of 10-20% by volume of the reaction solvent.
8. The method for preparing a two-dimensional diamond-shaped heterogeneous covalent organic framework according to claim 6, wherein the reaction conditions are as follows: standing for 3-7 days at 100-150 ℃.
9. The method for preparing a two-dimensional diamond shaped heterogeneous covalent organic framework material according to claim 7, further comprising a purification and drying step after the collection of solids, wherein the drying conditions are as follows: vacuum, 60-120 ℃; the purification mode adopts Soxhlet extraction.
10. The method for preparing the two-dimensional diamond-shaped heterogeneous covalent organic framework material according to claim 9, wherein the organic solvent used for washing comprises at least one of N, N-dimethylformamide DMF, tetrahydrofuran THF and Acetone acetate.
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