CN116854894A - Covalent organic framework material with three-dimensional structure and synthesis method thereof - Google Patents
Covalent organic framework material with three-dimensional structure and synthesis method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 31
- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 21
- 238000001308 synthesis method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- YBGIIZGNEOJSRF-UHFFFAOYSA-N 1-bromo-4-[tris(4-bromophenyl)methyl]benzene Chemical compound C1=CC(Br)=CC=C1C(C=1C=CC(Br)=CC=1)(C=1C=CC(Br)=CC=1)C1=CC=C(Br)C=C1 YBGIIZGNEOJSRF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 23
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- 101150003085 Pdcl gene Proteins 0.000 claims description 4
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- 238000001035 drying Methods 0.000 claims description 3
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- 239000011148 porous material Substances 0.000 abstract description 12
- 239000007787 solid Substances 0.000 abstract description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- PEQHIRFAKIASBK-UHFFFAOYSA-N tetraphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 PEQHIRFAKIASBK-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001917 fluorescence detection Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
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- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000002329 infrared spectrum Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000003795 desorption Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZZPNDIHOQDQVNU-UHFFFAOYSA-N 2-hydroxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound CC1(C)OB(O)OC1(C)C ZZPNDIHOQDQVNU-UHFFFAOYSA-N 0.000 description 2
- 238000003775 Density Functional Theory Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000005885 boration reaction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000004482 13C cross polarization magic angle spinning Methods 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XNNIJZZVUCWDJQ-UHFFFAOYSA-N C.BrC1=CC=CC=C1.BrC1=CC=CC=C1.BrC1=CC=CC=C1.BrC1=CC=CC=C1 Chemical compound C.BrC1=CC=CC=C1.BrC1=CC=CC=C1.BrC1=CC=CC=C1.BrC1=CC=CC=C1 XNNIJZZVUCWDJQ-UHFFFAOYSA-N 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229910003867 O—B—O Inorganic materials 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000013211 curve analysis Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- 239000000243 solution Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
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- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
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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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/124—Copolymers alternating
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
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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)
- Catalysts (AREA)
Abstract
The invention provides a covalent organic framework material with a three-dimensional structure and a synthesis method thereof, belonging to the field of synthesis of organic porous materials. The synthesis method comprises the following two steps: the first step is to take tetraphenyl methane and liquid bromine as raw materials to obtain light yellow powder solid tetra (4-bromophenyl) methane; the second step is to take tetra (4-bromophenyl) methane and 4, 7-bis (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) -2,1, 3-benzothiadiazole as raw materials, DMF as solvent and N 2 Under the condition of protecting and catalyst, the deep yellow powder COF-TBPM-BBT is synthesized by adopting an oil bath heating method, and the covalent organic framework material with a three-dimensional structure is prepared. The reaction has the advantages of simple synthesis process, mild reaction condition, high yield, strong thermal stability and chemical stability of the product and the like, and has wide application prospect in the fields of fluorescence detection, photocatalysis, electrocatalysis, environmental chemistry, pharmaceutical medical treatment and the like.
Description
The invention belongs to the field of synthesis of organic porous materials, and particularly relates to synthesis of a covalent organic framework material with a three-dimensional structure.
Background
The covalent organic framework material (covalent organic frameworks, COFs) is an organic porous material with ligand molecules connected by covalent bonds, and has the advantages of small mass density, large specific surface area, strong stability, rich pore channels and the like. At present, the research of constructing a two-dimensional covalent organic framework porous material is quite extensive, and the research of preparing a three-dimensional covalent organic framework material is limited due to great difficulty in ligand design and synthesis.
The most common ligands for constructing three-dimensional covalent organic framework materials are T d Symmetrical organic molecules, the connection mode for constructing three-dimensional covalent organic framework materials is mainly divided into [4+2 ]]、[4+3]、[4+4]Etc.
Disclosure of Invention
The invention aims to provide a novel porous covalent organic framework material with a three-dimensional structure and a synthesis method thereof, wherein a bromine-containing tetrahedral organic ligand and a boric acid pinacol ester-containing linear symmetrical construction unit are designed and synthesized, and a Miyaura boride reaction is adopted to construct the novel functional covalent organic framework material.
The organic ligand related by the invention is T d Symmetrical tetra (4-bromophenyl) methane and C 2 Symmetrical 4, 7-bis (4, 5-tetramethyl-1, 3, 2-dioxapentaborane-2-yl) -2,1, 3-benzothiadiazole, and the synthetic material is in the construction type of [4+2 ]]。
In order to achieve the above purpose, the invention adopts the following specific scheme:
a method of synthesizing a covalent organic framework material having a three-dimensional structure, comprising the steps of: the raw materials of tetra (4-bromophenyl) methane and 4, 7-bis # -, are mixedDissolving 4, 5-tetramethyl-1, 3, 2-dioxapentaborane-2-yl) -2,1, 3-benzothiadiazole in an organic solvent, adding an alkaline substance to provide an alkaline environment, and forming a mixed solution; the mixed solution is N 2 Under the protection and the action of a catalyst, stirring and reacting for 24-72 hours in an oil bath pot at 120-180 ℃, cooling to room temperature after the reaction is finished, filtering the precipitate, and washing, drying and grinding to obtain deep yellow COF-TBPM-BBT powder, namely the covalent organic framework material.
Wherein, firstly, preparing raw material tetra (4-bromophenyl) methane, wherein the tetra (4-bromophenyl) methane is prepared by the following steps: takes tetraphenyl methane and liquid bromine as raw materials, stir for 30min at room temperature, then slowly add C into the reaction mixture 2 H 5 OH, filtration and washing of the solid three times with ethanol gave tetrakis (4-bromophenyl) methane as a pale yellow solid.
Wherein the mass ratio of the tetra (4-bromophenyl) methane to the 4, 7-bis (4, 5-tetramethyl-1, 3, 2-dioxapentaborane-2-yl) -2,1, 3-benzothiadiazole is 1:1-1:3. In the embodiment of the invention, the specific selection is 1:1, 1:2 and 1:3, preferably 1:2.
Wherein the organic solvent is DMF, DMSO or 1,4-dioxane, preferably DMF.
Wherein the alkaline substance is K 2 CO 3 、KOAc、K 3 PO 4 Or KOH, preferably K 2 CO 3 。
Wherein the catalyst is Pd (PPh) 3 ) 4 、Pd(OAc) 2 Or PdCl 2 (dppf), preferably Pd (PPh) 3 ) 4 。
As a further optimization of the above synthesis method, the temperature of the reaction was 150℃and the time was 48 hours.
The invention further provides a covalent organic framework material with a three-dimensional structure synthesized by the synthesis method.
The beneficial effects are that: the invention takes tetra (4-bromophenyl) methane and 4, 7-bis (4, 5-tetramethyl-1, 3, 2-dioxapentaborane-2-yl) -2,1, 3-benzothiadiazole as raw materials, N' -dimethylformamide as solvent, N 2 Under the condition of protecting and catalyst, C is synthesized by adopting an oil bath heating methodThe OF-TBPM-BBT dark yellow powder is a covalent organic framework material polymer with a three-dimensional structure, and the reaction has the characteristics OF simple synthesis process, mild reaction conditions, high yield, high thermal stability OF products, strong chemical stability and the like, and has potential application prospects in the fields OF fluorescence detection, photocatalysis, electrocatalysis, environment, medical treatment and the like.
Drawings
FIG. 1 is a synthetic route diagram of a COF-TBPM-BBT material synthesized in accordance with the present invention;
FIG. 2 is an infrared spectrum of the COF-TBPM-BBT material synthesized by the invention;
FIG. 3 shows the solid nuclear magnetism of the COF-TBPM-BBT material synthesized by the invention 13 C, spectrogram;
FIG. 4 is a graph showing nitrogen desorption and elution of the COF-TBPM-BBT material synthesized by the invention;
FIG. 5 is a pore size distribution diagram of a COF-TBPM-BBT material synthesized according to the present invention;
FIG. 6 is a scanning electron microscope image of the COF-TBPM-BBT material synthesized by the invention;
FIG. 7 is an enlarged view of a scanning electron microscope of the COF-TBPM-BBT material synthesized by the invention;
FIG. 8 is a thermogravimetric analysis of the synthesized COF-TBPM-BBT material of the present invention;
FIG. 9 is an X-ray photoelectron spectrum of a COF-TBPM-BBT material synthesized according to the present invention.
Detailed Description
Synthesis of COF-TBPM-BBT: dissolving tetra (4-bromobenzene) methane and 4, 7-bis (4, 5-tetramethyl-1, 3, 2-dioxapentaborane-2-yl) -2,1, 3-benzothiadiazole in DMF, stirring the mixed solution in an oil bath kettle at 120-180 ℃ for reaction for 12-72 hours; after the reaction is finished, standing and naturally cooling, carrying out suction filtration, washing unreacted raw materials of a product by using DMF, washing the DMF by using distilled water, fully washing by using tetrahydrofuran and acetone, carrying out vacuum drying at 100 ℃ for 24 hours after washing is finished, and grinding to obtain deep yellow powder which is the target product.
The mass ratio of the tetra (4-bromophenyl) methane to the 4, 7-bis (4, 5-tetramethyl-1, 3, 2-dioxapentaborane-2-yl) -2,1, 3-benzothiadiazole is 1:1-1:3.
The synthetic reaction equation for COF-TBPM-BBT is as follows:
。
the technical scheme of the invention will be clearly and completely described in the following in connection with the embodiments of the invention.
Example 1
Tetrakis (4-bromophenyl) methane (127.20 mg,0.15 mmol), 4, 7-bis (4, 5-tetramethyl-1, 3, 2-dioxapentaborane-2-yl) -2,1, 3-benzothiadiazole (116.43 mg,0.3 mmol) and anhydrous K 2 CO 3 (247 mg,1.8 mmol) was dissolved in 9ml anhydrous N, N' -dimethylformamide, then the catalyst tetrakis (triphenylphosphine) palladium (4 mg, 3.4. Mu. Mol) was rapidly added to the solution, and N 2 And (3) protecting, stirring the mixed solution in an oil bath at 150 ℃ for 48 hours, stopping the reaction, naturally standing, cooling to room temperature, performing suction filtration, washing the product with DMF, washing unreacted raw materials of tetra (4-bromophenyl) methane and 4, 7-bis (4, 5-tetramethyl-1, 3, 2-dioxapentaborane-2-yl) -2,1, 3-benzothiadiazole and oligomers, washing residual DMF molecules on the surface and in a pore canal of a sample with distilled water, and finally washing the product with tetrahydrofuran and acetone fully. Filtering to obtain precipitate, drying at 100deg.C for 24 hr, and grinding to obtain COF-TBPM-BBT as dark yellow powdery solid with product yield of 90% and specific surface area of 249m 2 /g。
Example 2
In example 1, other conditions are kept unchanged, and increasing the ratio of the monomers of the boric acid pinacol ester group (the mass ratio of the substances is 1:3) or increasing the ratio of the ligands of the tetra (4-bromophenyl) methane (the mass ratio of the substances is 1:1) can lead excessive groups to fully carry out coupling reaction with the groups of the other ligands, but unreacted groups are exposed on the surface of the material and are not easy to separate from reaction products, so that the mass density of the reaction products is increased, and raw materials are wasted. Thus, the ratio of the amounts of tetrakis (4-bromophenyl) methane and 4, 7-bis (4, 5-tetramethyl-1, 3, 2-dioxapentaborane-2-yl) -2,1, 3-benzothiadiazole species should be controlled to be 1:2 in terms of the ratio of groups of the ligand that participate in the boration reaction, without adjustment.
Example 3
While the other conditions in example 1 were maintained and the reaction temperature was increased to 180 ℃, the reaction was found to complete more rapidly and at a faster rate, but the catalyst was destroyed at a higher temperature and the activity was reduced, while the product appeared dark brown with little precipitate as the reaction proceeded further. The specific surface area is reduced by measurement, because the reaction at higher temperature for a long time can change or even destroy the structure of the already formed microporous particles, which is unfavorable for the generation of products. Therefore, the reaction temperature should be controlled between 120 and 180 ℃.
Example 4
While keeping the other conditions unchanged in example 1, the reaction time was prolonged to 72h, and it was found that the reaction product appeared dark brown and less precipitate as in example 3. The specific surface area is smaller, because a good micropore structure is formed after the reaction is carried out for about 48 hours, and the formed micropore structure is destroyed in a reaction system along with the increase of the reaction time, so that carbonization occurs, and the maintenance of the pore structure of a product is not facilitated. Therefore, the reaction time should be controlled at 48 hours.
Example 5
While keeping the other conditions unchanged in example 1, using DMSO,1,4-dioxane as the reaction solvent, it was found that longer time was required for the product formation. This is because when DMSO,1,4-dioxane is used as a reaction solvent, the reactants tetrakis (4-bromophenyl) methane and 4, 7-bis (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) -2,1, 3-benzothiadiazole are poor in solubility, slow in reaction rate, and reduced in yield. Therefore, DMF was chosen as the reaction solvent.
Example 6
The other conditions in example 1 were kept unchanged, KOAc, K were selected 3 PO 4 KOH to provide an alkaline environment for the reaction when K is used 3 PO 4 Where KOAc, KOH provides the alkaline environment required for the reaction, the product formation rate is found to be slow and the yield is low. This is because the pH value has a large influence on the boration reaction and the activity of the catalyst, and it is known from the examination of data and calculation that: KOAc provides a pH of 11.28, K 3 PO 4 Provides a pH of 12.59, KOH provides a pH of 13.30, K 2 CO 3 The pH value is provided to be 11.78, and the experiment result shows that the pH value of the reaction is preferably 11-12, namely KOAc or K 2 CO 3 Proper acid and alkali, combined cost and better pH value, K is selected 2 CO 3 To provide a more suitable alkaline environment for the reaction.
Example 7
Pd (OAc) was chosen to maintain the other conditions of example 1 unchanged 2 、PdCl 2 (dppf) as a catalyst for the reaction, it was found that the product formation took longer and the yield was lower. This is because Pd (OAc) 2 、PdCl 2 The (dppf) decreases the activation energy of the reaction less, resulting in not increasing the reaction rate much, and the structure of the catalyst is destroyed under the reaction temperature and alkaline environment, resulting in decreasing the activity of the catalyst. Therefore, pd (PPh) 3 ) 4 As a catalyst for this reaction.
Performance analysis was performed on the COF-TBPM-BBT synthesized in example 1.
FIG. 1 is a synthetic route diagram of the COF-TBPM-BBT materials synthesized by the present invention.
FT-IR analysis: FIG. 2 is a FT-IR analysis chart of the materials TBPM and BBT and the product COF-TBPM-BBT used in the present invention, the brown line is the infrared spectrum of TBPM, 1076 cm -1 The absorption peak at this point is the flexural vibration peak of the C-Br bond, 532 cm -1 And 512 cm -1 The absorption peak at the position is the stretching vibration peak of the C-Br bond; the rose color line is BBT infrared spectrum, 3620 and 3620 cm -1 And 3545 cm -1 The absorption peak at the position is the stretching vibration peak of the O-B-O bond, 2982 cm -1 And 2932 cm -1 The absorption peak at this point is methyl (-CH) 3 ) Asymmetric stretching vibration peaks of (2); the black line is the infrared spectrum of COF-TBPM-BBT, compared with the infrared spectrum of TBPM, 532 cm -1 And 512 cm -1 The two characteristic absorption peaks at the position completely disappear in the COF-TBPM-BBT, and prove that all TBPM participates in the polymerization reaction, and compared with the infrared spectrum of the BBT, the infrared spectrum of the BBT shows that 3620 cm -1 And 3545 cm -1 Both characteristic absorption peaks at the position completely disappeared in COF-TBPM-BBT, patternAll BBTs are known to participate in the polymerization reaction. The product synthesized according to the invention is located at 1485 cm -1 、1005 cm -1 、808 cm -1 Three characteristic absorption peaks at which correspond to c=c, respectively p-Ar Is stretched out and drawn back to vibrate, C sp 3 -C Ar In-plane bending vibrations of C-H, the occurrence of these three signal characteristic peaks demonstrates the structural integrity of the product.
13 C solid nuclear magnetic test: FIG. 3 shows the nuclear magnetic resonance spectrum of the solid high resolution magic angle for the present invention 13 C CPMAS-NMR characterizes the structural features of COF-TBPM-BBT. The peak at a peak value of 64.97 ppm corresponds to sp on the tetraphenyl methane skeleton 3 Carbon of the hybrid orbit; the peak with the peak value of about 130.00 ppm corresponds to sp on benzene ring under different environments 2 Carbon of the hybrid orbit; the peak at the peak value of 146.28 ppm corresponds to carbon at positions 2, 5 of the benzene ring; the peak at the peak value of 153.87 ppm corresponds to sp of the benzene ring linked to the thiophene ring 2 Carbon at the site.
Nitrogen adsorption and desorption curve analysis: FIG. 4 is a graph showing adsorption and desorption isotherms of nitrogen (molecular size 3.64A) of COF-TBPM-BBT at 77K, with open circles as adsorption isotherms and filled circles as desorption isotherms; fig. 5 is a pore size distribution of COF-TBPM-BBT calculated using DFT method according to nitrogen adsorption-desorption isotherm. In the research process, after the structure of the organic porous material is determined, the characteristics of the porous characteristics, specific surface area and the like of the organic porous material need to be characterized. The operation is as follows: the sample powder was first ground thoroughly and dried in vacuo at 120 ℃ for 12 hours to remove guest solvent molecules in the framework channels before testing, and then nitrogen adsorption-desorption test experiments were performed on COF-TBPM-BBT at 77K, and the product was found to have a typical type i gas adsorption profile, indicating the presence of a microporous structure in COF-TBPM-BBT. Analysis of fig. 4 reveals that the adsorption curve rises slowly and the desorption curve lags, and the reference suggests that this phenomenon is caused by the unique swelling characteristics of the organic framework. BET specific surface area of COF-TBPM-BBT is 249m 2 ∙g -1 The pore size distribution of the microporous material is uniform according to the analysis of a density-generalized enthalpy theory (DFT) model.
Scanning electron microscope analysis: fig. 6 and 7 are scanning electron microscope diagrams of COF-TBPM-BBT synthesized by the invention, and Scanning Electron Microscope (SEM) characterization is performed in order to better observe the properties of the COF-TBPM-BBT, such as morphology, internal structure, particle size, uniformity, and the like. It can be found that the COF-TBPM-BBT formed by coupling polymerization of the tetrahedral structure building blocks and the linear structure building units is relatively uniform in size, has a spherical morphology, has a rough structure surface and loose texture, has a particle size of about 500 nanometers, and has a certain degree of agglomeration, which is similar to most three-dimensional porous organic frame materials in reported documents. This is probably due to the high degree of cross-linking of the polymer, the liquid-liquid phase separation occurring in the oligomer stage of the reaction, the further reaction of the monomer in the system with the abundant oligomer droplets, and the final product having a uniform spherical morphology.
Thermal stability test: FIG. 8 shows the results of the thermal stability test of the present invention, which were carried out by washing with DMF, concentrated hydrochloric acid, water, tetrahydrofuran and acetone in this order during the post-treatment of the sample to remove the catalyst, low-aggregation and unreacted monomer. We also tried to dissolve COF-TBPM-BBT with the more polar organic solvents common in laboratories such as ethyl acetate, dichloromethane, methanol, DMF and DMAc, and found that it was poorly soluble in the above organic solvents. To investigate the thermal stability of COF-TBPM-BBT, samples were heated to 800 ℃ in a nitrogen atmosphere, the decomposition temperature of COF-TBPM-BBT was as high as 540 ℃, the mass fraction was reduced by 10.07% when the temperature was 580 ℃, and the residual mass fraction was as high as 81.13% when the temperature was increased to 795 ℃, all of which demonstrated that the product had higher thermal stability. Through the experiment, the COF-TBPM-BBT has good chemical stability and thermal stability.
XPS analysis: FIG. 9 is an X-ray photoelectron spectrum (XPS) of the COF-TBPM-BBT synthesized by the invention, which is an electron spectrum based on the photoelectric effect, and is also called as chemical analysis Electron Spectrum (ESCA). XPS spectrogram shows that COF-TBPM-BBT is mainly composed of carbon, nitrogen and sulfur elements, and the peaks and theoretical values of experimental curves of C1S, N1S, S2S and S2 p spectrograms are close. XPS, FT-IR, solid 13 The results of both C-NMR and SEM are sufficient to demonstrate COF-TStructural integrity of BPM-BBT.
It should be noted that the above-mentioned embodiments are to be understood as illustrative, and not limiting, the scope of the invention, which is defined by the appended claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made to the present invention without departing from its spirit or scope.
Claims (10)
1. A method for synthesizing a covalent organic framework material with a three-dimensional structure, which is characterized by comprising the following steps: the synthesis method comprises the following steps: dissolving raw materials of tetra (4-bromophenyl) methane and 4, 7-bis (4, 5-tetramethyl-1, 3, 2-dioxapentaborane-2-yl) -2,1, 3-benzothiadiazole in an organic solvent, and adding an alkaline substance to provide an alkaline environment to form a mixed solution; the mixed solution is N 2 Under the protection and the action of a catalyst, stirring and reacting for 24-72 hours in an oil bath pot at 120-180 ℃, cooling to room temperature after the reaction is finished, filtering the precipitate, and washing, drying and grinding to obtain deep yellow COF-TBPM-BBT powder, namely the covalent organic framework material.
2. The synthesis method according to claim 1, wherein: the mass ratio of the tetra (4-bromophenyl) methane and the 4, 7-bis (4, 5-tetramethyl-1, 3, 2-dioxapentaborane-2-yl) -2,1, 3-benzothiadiazole is 1:1-1:3.
3. The synthesis method according to claim 2, characterized in that: the mass ratio of the tetra (4-bromophenyl) methane and the 4, 7-bis (4, 5-tetramethyl-1, 3, 2-dioxapentaborane-2-yl) -2,1, 3-benzothiadiazole is 1:2.
4. The synthesis method according to claim 1, wherein: the organic solvent is DMF, DMSO or 1,4-dioxane.
5. The method of synthesis according to claim 4, wherein: the organic solvent is DMF.
6. The synthesis method according to claim 1, wherein: the alkaline substance is K 2 CO 3 、KOAc、K 3 PO 4 Or KOH.
7. The synthesis method according to claim 1, wherein: the catalyst is Pd (PPh) 3 ) 4 、Pd(OAc) 2 Or PdCl 2 (dppf)。
8. The method of synthesis according to claim 7, wherein: the catalyst is Pd (PPh) 3 ) 4 。
9. The synthesis method according to claim 1, wherein: the reaction temperature was 150℃and the reaction time was 48 hours.
10. Covalent organic framework materials having a three-dimensional structure synthesized by the synthesis method according to any one of claims 1 to 9.
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