CN111635523A - Two-dimensional covalent organic framework material with trimeric quinazoline as junction, preparation method and application thereof - Google Patents
Two-dimensional covalent organic framework material with trimeric quinazoline as junction, preparation method and application thereof Download PDFInfo
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- CN111635523A CN111635523A CN202010492325.1A CN202010492325A CN111635523A CN 111635523 A CN111635523 A CN 111635523A CN 202010492325 A CN202010492325 A CN 202010492325A CN 111635523 A CN111635523 A CN 111635523A
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 75
- 239000000463 material Substances 0.000 title claims abstract description 39
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- DJVJDQRJKTVAEU-UHFFFAOYSA-N 2,5-diaminobenzene-1,4-dicarbonitrile Chemical compound NC1=CC(C#N)=C(N)C=C1C#N DJVJDQRJKTVAEU-UHFFFAOYSA-N 0.000 claims abstract description 15
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 14
- 238000001179 sorption measurement Methods 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims abstract description 10
- 239000005431 greenhouse gas Substances 0.000 claims abstract description 10
- 238000001570 ionothermal synthesis Methods 0.000 claims abstract description 8
- 239000011592 zinc chloride Substances 0.000 claims abstract description 7
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 26
- -1 hydrogen ions Chemical class 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 10
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical group C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 claims description 9
- UCRQGBRIGDKUAM-UHFFFAOYSA-N 2,5-dichlorobenzene-1,4-dicarbonitrile Chemical compound ClC1=CC(C#N)=C(Cl)C=C1C#N UCRQGBRIGDKUAM-UHFFFAOYSA-N 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- 238000006722 reduction reaction Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 239000007983 Tris buffer Substances 0.000 claims description 5
- SXZIXHOMFPUIRK-UHFFFAOYSA-N diphenylmethanimine Chemical compound C=1C=CC=CC=1C(=N)C1=CC=CC=C1 SXZIXHOMFPUIRK-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000003446 ligand Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003463 adsorbent Substances 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- 239000013317 conjugated microporous polymer Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 claims 1
- 230000003993 interaction Effects 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 3
- 238000005411 Van der Waals force Methods 0.000 abstract description 2
- 229920000620 organic polymer Polymers 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007872 degassing Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0633—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring
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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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/063—Polymers comprising a characteristic microstructure
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- B01J35/33—
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Abstract
The invention belongs to the field of porous organic polymers, and discloses a two-dimensional covalent organic framework material (COFs) taking trimeric quinazoline as a node and a preparation method thereof, wherein the COFs is prepared by taking 1, 4-diamino-2, 5-dicyanobenzene under the protection of inactive gas, carrying out catalytic action of anhydrous zinc chloride and carrying out ionothermal synthesis; the invention also discloses an application of the two-dimensional covalent organic framework material with the trimeric quinazoline as a node in the adsorption of greenhouse gases or the preparation of hydrogen energy by electrocatalysis hydrogen evolution. The COFs prepared by the method has higher porosity and stronger electronegativity of N atoms, can provide more storage spaces for the adsorption of greenhouse gases, and can form a one-dimensional channel through the interaction of Van der Waals force between layers, thereby effectively promoting the rapid conduction of H ions and improving the catalytic hydrogen evolution performance of the H ions; the prepared COFs are used for adsorbing greenhouse gases or used for preparing hydrogen energy by electrocatalytic hydrogen evolution.
Description
Technical Field
The invention belongs to the field of porous organic polymers, and relates to a two-dimensional covalent organic framework material, in particular to a two-dimensional covalent organic framework material taking trimeric quinazoline as a node, and a preparation method and application thereof.
Background
Two-dimensional covalent organic framework materials (COFs) are a long-range ordered porous crystalline material, have the advantages of high order, adjustable pore diameter, large specific surface area, various synthetic methods, easy functional modification and the like, and are a new heterogeneous catalyst. In the process of preparing the COFs, the shape, the size and the surface property of the COFs are regulated and controlled by a construction module, so that the multifunctional application of the COFs material is realized, and the method is always an investigation in the field of porous organic polymersFind out the hot spot. The trimeric quinazoline is a planar molecule with a conjugated structure, contains abundant N atoms, has strong electronegativity and can react with greenhouse gases (such as CO)2And CH4) Forming stronger interaction and realizing the rapid migration of electrons on the surface.
Disclosure of Invention
The invention aims to provide a two-dimensional covalent organic framework material with trimeric quinazoline as a node, which can be used for adsorbing greenhouse gases and electrically catalyzing and separating hydrogen;
the invention also aims to provide a preparation method of the two-dimensional covalent organic framework material with the trimeric quinazoline as a node;
it is a further object of the present invention to provide the use of the above-mentioned trimeric quinazoline-linked two-dimensional covalent organic framework materials.
In order to achieve the purpose, the invention adopts the technical scheme that:
a two-dimensional covalent organic framework material with trimeric quinazoline as a node has the following chemical structural formula:
the invention also provides a preparation method of the two-dimensional covalent organic framework material with the trimeric quinazoline as the node, which is to take 1, 4-diamino-2, 5-dicyanobenzene to carry out ionothermal synthesis under the protection of inactive gas through the catalysis of anhydrous zinc chloride.
In one embodiment, after completion of the ionothermal synthesis, the mixture is further washed with an aqueous solution of an inorganic acid and an alcohol solvent.
By way of further limitation, the molar ratio of 1, 4-diamino-2, 5-dicyanobenzene to anhydrous zinc chloride is 1: 0.5 to 2;
the reaction temperature during the ionothermal synthesis is increased from room temperature to 350-450 ℃, the heating rate is 5 ℃/min, and the reaction time is 36-72 h;
the inorganic acid aqueous solution is hydrochloric acid aqueous solution, nitric acid aqueous solution or sulfuric acid aqueous solution;
the alcohol solvent is methanol, ethanol or isopropanol;
the concentration of hydrogen ions in the aqueous solution of the inorganic acid is 0.5 to 2 mol/L.
As another limitation, the process for the preparation of 1, 4-diamino-2, 5-dicyanobenzene comprises the following steps carried out in sequence:
a1) under the protection of inactive gas, taking (+/-) -2,2 '-bis (diphenylphosphino) -1, 1' -binaphthyl (rac-BINAP) and tris (dibenzylidene-BASE acetone) dipalladium (Pd)2(dba)3) Dissolving in organic solvent, cooling to room temperature, adding 2, 5-dichloroterephthalonitrile and benzophenone imine (Ph)2Performing reflux reaction on the reaction product of the reaction product and sodium tert-butoxide, and then separating and purifying to obtain 2, 5-bis ((diphenylmethylene) amino) terephthalonitrile;
a2) dissolving 2, 5-bis ((diphenylmethylene) amino) terephthalonitrile in tetrahydrofuran, adding hydrochloric acid water solution, carrying out reduction reaction, and separating and purifying to obtain 1, 4-diamino-2, 5-dicyanobenzene hydrochloride;
a3) adding 1, 4-diamino-2, 5-dicyanobenzene hydrochloride into an aqueous solution of sodium hydroxide, performing neutralization reaction, and separating and purifying to obtain the 1, 4-diamino-2, 5-dicyanobenzene;
the chemical reaction formula of the preparation process is as follows:
in the step a 1), the separation and purification includes cooling to room temperature after the reflux reaction is finished, and purifying by column chromatography to obtain 2, 5-bis ((diphenylmethylene) amino) terephthalonitrile;
in the step a 2), the separation and purification is to concentrate and remove the solvent after the reduction reaction is finished to obtain a crude product of 1, 4-diamino-2, 5-dicyanobenzene hydrochloride, wash the crude product with n-hexane, filter and dry the crude product to obtain the 1, 4-diamino-2, 5-dicyanobenzene hydrochloride;
in the step a 3), the separation and purification includes adding ethyl acetate for extraction after the neutralization reaction is finished, separating phases, drying the obtained ethyl acetate phase through anhydrous sodium sulfate, filtering, concentrating to remove the solvent, and drying to obtain the 1, 4-diamino-2, 5-dicyanobenzene.
As a further limitation, in step a 1), the eluent for column chromatography is a mixture of solvents with a volume ratio of 1: 0.5-6 of a mixed solution of ethyl acetate and petroleum ether.
As a further limitation, in the step a 1), the temperature for combining the catalyst and the ligand is 40-120 ℃ and the time is 1.5-3 h;
the time of the reflux reaction is 36-72 h;
in the step a 2), the temperature of the reduction reaction is 20-50 ℃ and the time is 8-20 h;
in the step a 3), the temperature of the neutralization reaction is 0-50 ℃ and the time is 0.5-3 h.
As a further limitation, in step a 1), the organic solvent is toluene, ethyl acetate or dichloromethane;
the molar ratio of (+ -) -2,2 '-bis (diphenylphosphino) -1, 1' -binaphthyl to tris (dibenzylidene-BASE acetone) dipalladium is 1: 0.25 to 1;
the weight ratio of the 2, 5-dichloro-terephthalonitrile, the benzophenone imine and the sodium tert-butoxide is 1: 1-4: 1-6;
and (3) taking (+/-) -2,2 '-bis (diphenylphosphino) -1, 1' -binaphthyl as a ligand, wherein the general addition amount is that the weight ratio of (+/-) -2,2 '-bis (diphenylphosphino) -1, 1' -binaphthyl to 2, 5-dichloro-terephthalonitrile is 0.4-0.6: 1;
the weight volume ratio of the 2, 5-dichloro-terephthalonitrile to the organic solvent is 1 kg: 15-65L;
in step a 2), the weight to volume ratio of 2, 5-bis ((diphenylmethylene) amino) terephthalonitrile to tetrahydrofuran was 1 kg: 20-50L;
the concentration of the hydrochloric acid aqueous solution is 1-2 mol/L;
the molar ratio of the 2, 5-bis ((diphenylmethylene) amino) terephthalonitrile to the hydrochloric acid in the aqueous hydrochloric acid solution is 1: 2-4;
in the step a 3), the concentration of the sodium hydroxide aqueous solution is 0.5-1.2 mol/L;
the mol ratio of the 1, 4-diamino-2, 5-dicyanobenzene hydrochloride to the sodium hydroxide is 1:1 to 4.
The invention also provides an application of the two-dimensional covalent organic framework material with the trimeric quinazoline as a node, and the nitrogen-containing conjugated microporous polymer network loaded molybdenum disulfide composite material is used as an adsorbent for adsorbing greenhouse gases (such as CH)4、CO2) (ii) a Or as a catalyst for electrocatalytic hydrogen evolution reaction.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the technical progress that:
the two-dimensional covalent organic framework material which is prepared by taking the trimeric quinazoline as the node and takes the trimeric quinazoline as the node has a larger pore structure, and the two-dimensional covalent organic framework material is connected through a chemical bond (C-N, C-C, C = N), so that the physical and chemical stability of the structure can be obviously improved. The two-dimensional covalent organic framework material taking trimeric quinazoline as a node has larger porosity and stronger electronegativity of N atom, and can be CO2And CH4The adsorption of the greenhouse gases provides more storage space and can also enhance the interaction force with the gas molecules. The surface of the two-dimensional covalent organic framework material taking the trimeric quinazoline as a node has rich conjugated structure, can effectively promote the rapid migration of electrons, and effectively promotes H through the one-dimensional channel formed by the interaction of Van der Waals force between layers+The ions are quickly conducted, so that the ions can be used as a catalyst for the electro-catalytic hydrogen evolution reaction, and the efficiency of the electro-catalytic hydrogen evolution reaction is effectively improved;
the preparation method provided by the invention adopts industrial raw materials, has low production cost, is green and has no pollution; the preparation method is simple, convenient to operate, controllable in process and suitable for industrial production, and the prepared two-dimensional covalent organic framework material taking the trimeric quinazoline as a node is used as an adsorbent for adsorbing greenhouse gases; or as a catalyst for preparing hydrogen energy in the electrocatalytic hydrogen evolution reaction.
Drawings
FIG. 1 is a set of COFs prepared in example 1 and measured in example 10 of the present invention1CH (A) of4And CO2The gas of (1 bar, 273K);
FIG. 2 COFs prepared in example 1 and measured in example 10 of the present invention1And a voltammetric linear scan curve of Pt 20%.
Detailed Description
The present invention is further illustrated by the following specific examples, which are to be construed as merely illustrative, and not limitative of the remainder of the disclosure.
In the following examples, all reagents were commercially available unless otherwise specified, and the experimental procedures were carried out according to the conventional experimental procedures unless otherwise specified.
Example 1 preparation method of two-dimensional covalent organic framework material using trimeric quinazoline as junction
The specific preparation process of the two-dimensional covalent organic framework material with trimeric quinazoline as a junction in this embodiment includes the following steps in sequence:
1) preparation of 1, 4-diamino-2, 5-dicyanobenzene
a1) Under the protection of nitrogen, 5kg (8 mol) of (+/-) -2,2 '-bis (diphenylphosphino) -1, 1' -binaphthyl (rac-BINAP) and 3.66kg (4 mol) of tris (dibenzylidene-BASE acetone) dipalladium (Pd)2(dba)3) Dissolving in 200L of anhydrous toluene to form a black red solution, and heating from room temperature to 110 ℃ to react for 2h while stirring, so that the catalyst is combined with the ligand. And cooling to room temperature after the reaction is finished, sequentially adding 10kg of 2, 5-dichloroterephthalonitrile, 22.8kg of benzophenone imine and 12.7kg of sodium tert-butoxide, heating to reflux, carrying out reflux reaction for 36h, purifying the reacted solution by using silica gel column chromatography after the reaction is finished, wherein the eluent is a compound with the volume ratio of 1: 4, purifying, evaporating the solvent, and vacuum drying at 60 ℃ for 3h to obtain 19.2kg of 2, 5-bis ((diphenylmethylene) amino) terephthalonitrile (molecular weight is 486) with yield of 78%.
a2) Dissolving 6kg of 2, 5-bis ((diphenylmethylene) amino) terephthalonitrile in 150L of tetrahydrofuran, dropwise adding 15L of hydrochloric acid aqueous solution with the concentration of 2mol/L for 1h, stirring at 25 ℃ to perform reduction reaction for 8h, concentrating to remove the solvent tetrahydrofuran after the reaction is finished, sequentially washing with 50L of n-hexane and 50L of diethyl ether for three times respectively, stirring for 10min each time, filtering, and vacuum drying at 60 ℃ for 3h to obtain 2.78kg of 1, 4-diamino-2, 5-dicyanobenzene hydrochloride (with the molecular weight of 231), wherein the yield is 98%;
a3) adding 2.5kg of 1, 4-diamino-2, 5-dicyanobenzene hydrochloride into 50L of sodium hydroxide aqueous solution with the concentration of 0.5mol/L, stirring at 25 ℃ for neutralization reaction for 1h, adding 25L of ethyl acetate for extraction, separating phases, drying the obtained ethyl acetate phase by anhydrous sodium sulfate to remove excessive water, filtering, concentrating to remove solvent ethyl acetate, and vacuum drying at 80 ℃ for 12h to obtain 1.6kg of 1, 4-diamino-2, 5-dicyanobenzene with the yield of 93%.
The chemical reaction formula for preparing 4-diamino-2, 5-dicyanobenzene is as follows:
2) preparation of two-dimensional covalent organic framework material with trimeric quinazoline as junction
Under the protection of nitrogen, 1.58kg (10 mol) of 1, 4-diamino-2, 5-dicyanobenzene and 1.36kg (10 mol) of anhydrous zinc chloride are mixed, then the mixture is placed in a tubular furnace to be heated from room temperature to 400 ℃ at a constant speed at the heating rate of 5 ℃/min, the temperature is kept at 400 ℃ for reaction for 36 hours, after the reaction is finished, the mixture is cooled to room temperature, and a product is ground to have the particle size of 500nm, so that 2.53kg of a crude product is obtained. Washing the crude product with 20L hydrochloric acid water solution with concentration of 1mol/L, 20L anhydrous ethanol, and 20L acetone respectively for three times, vacuum drying at 120 deg.C for 48h to obtain 1.48kg two-dimensional covalent organic framework material (COFs for short) with trimeric quinazoline as node1）。
The two-dimensional covalent organic framework material with the trimeric quinazoline as the node, which is prepared by the embodiment, can be used as an adsorbent for adsorbing greenhouse gases, and can also be used as a catalyst for preparing an electrocatalytic hydrogen evolution reaction of hydrogen energy.
Example 2-9 preparation of two-dimensional covalent organic framework materials with Tripolyquinazoline as the junction
Examples 2 to 9 are methods for preparing a two-dimensional covalent organic framework material using trimeric quinazoline as a node, and the steps are substantially the same as those in example 1, except for differences in process parameters, which are specifically shown in table 1:
TABLE 1 summary of the process parameters of examples 2 to 9
The contents of the other portions of examples 2 to 9 are the same as those of example 1.
Example 10 Performance testing of a two-dimensional covalent organic framework Material with Triquinazolines as a node
COFs prepared in comparative examples 1 to 41~ COFs4The crystal form performance of the compound shows that the COFs prepared by 1, 4-diamino-2, 5-dicyanobenzene and anhydrous zinc chloride in a molar ratio of 1:11The crystal form performance of the compound is best;
COFs prepared in comparative example 11And COFs prepared in example 55COFs prepared in example 77Crystalline Properties of (1), COFs prepared in comparative example 22And COFs prepared in example 66COFs prepared in example 88Crystalline Properties of (1), COFs prepared in comparative example 44And COFs prepared in example 99The crystal form performance of the prepared COFs is the best when the reaction temperature is 400 ℃ during the ionothermal synthesis;
COFs prepared in example 11Carrying out CO2And CH4Experiment of gas adsorption, 5g of COFs was taken1Placing the sample in a degassing tube, degassing at 150 deg.C for 12 hr, and degassing COFs1The degassing tubes of the samples were connected to a Congta gas adsorber for testing, see FIG. 1, at 273K (Kelvin temperature, phase)At 0 ℃) under 1bar, CO2Adsorption capacity 16.2wt%, CH4The adsorption amount was 1.77 wt%;
COFs prepared in example 1 were measured using a Princeton electrochemical workstation scanning linear voltammograms at a scan rate of 5mV/s over a range of 0 to-1V1At a current density of 10, see fig. 2, the overpotential is 80 mV;
when the current density of 20% Pt/C is 10, see FIG. 2, the overpotential is 50mV, and the overpotential is small, so that the energy consumption is small in the process of catalytically evolving hydrogen, therefore, the existing catalytic hydrogen evolution generally adopts 20% Pt/C as a catalyst to electrically catalyze hydrogen evolution. The overpotential of the COFs prepared by the method is close to 20% of Pt/C, the structure of the COFs based on the trimeric quinazoline as a node can improve the stability of the COFs under an acidic condition, and a full conjugate plane formed by the structure can effectively promote the delocalization effect of electrons and improve the conductivity of the material. When the COFs is used for electrocatalytic hydrogen evolution, the prepared COFs can ensure that the electrocatalytic reaction can trigger the hydrogen evolution reaction under lower driving current, so that the hydrogen evolution energy consumption is reduced, and meanwhile, the quick adsorption and release of hydrogen can be realized, so that higher hydrogen evolution efficiency and higher hydrogen production quantity are obtained, and the hydrogen evolution effect is obviously improved.
COFs prepared in examples 2 to 92~ COFs9Carrying out CO2And CH4Gas adsorption experiments were carried out with CO at 273K (Kelvin, corresponding to 0 ℃) at 1bar2Adsorption amount and CH4The adsorption amounts are shown in Table 2; COFs prepared in examples 2 to 92~COFs9The sweep voltammograms were almost the same as those measured in examples 2 to 9 and example 1, and thus no difference was observed in fig. 2, which is not shown in fig. 2. COFs prepared in examples 2 to 9 at a current density of 102~COFs9See table 2 for values of overpotential of:
TABLE 2 summary of the results of the measurements in examples 2 to 9
It should be noted that the embodiments 1 to 9 are only preferred embodiments of the present invention, and are not intended to limit the present invention in other forms, and any person skilled in the art may use the above technical contents as a teaching to make changes or modifications to the equivalent embodiments with equivalent changes, but all those simple changes, equivalent changes and modifications made to the above embodiments without departing from the technical spirit of the present invention, and still all those embodiments fall within the scope of the present invention.
Claims (10)
1. The two-dimensional covalent organic framework material with the trimeric quinazoline as the node is characterized in that the chemical structural formula of the two-dimensional covalent organic framework material with the trimeric quinazoline as the node is as follows:
2. a method for preparing a two-dimensional covalent organic framework material with trimeric quinazoline as a node in claim 1, which is characterized in that the preparation method comprises the steps of taking 1, 4-diamino-2, 5-dicyanobenzene to perform ionothermal synthesis under the protection of inactive gas through the catalysis of anhydrous zinc chloride.
3. The method for preparing a trimeric quinazoline as a joint two-dimensional covalent organic framework material according to claim 2, wherein after the completion of the ionothermal synthesis, the washing with an inorganic acid aqueous solution and an alcohol solvent is further required.
4. The method for preparing trimeric quinazoline knotted two-dimensional covalent organic framework material of claim 3,
the molar ratio of the 1, 4-diamino-2, 5-dicyanobenzene to the anhydrous zinc chloride is 1: 0.5 to 2;
the reaction temperature during the ionothermal synthesis is increased from room temperature to 350-450 ℃, the heating rate is 5 ℃/min, and the reaction time is 36-72 h;
the inorganic acid aqueous solution is hydrochloric acid aqueous solution, nitric acid aqueous solution or sulfuric acid aqueous solution;
the alcohol solvent is methanol, ethanol or isopropanol;
the concentration of hydrogen ions in the aqueous solution of the inorganic acid is 0.5 to 2 mol/L.
5. A method for the preparation of a trimeric quinazoline bonded two-dimensional covalent organic framework material according to any of the claims 2 to 4, characterized in that the process for the preparation of 1, 4-diamino-2, 5-dicyanobenzene comprises the following steps performed in sequence:
a1) under the protection of inactive gas, dissolving (+/-) -2,2 '-bis (diphenylphosphino) -1, 1' -binaphthyl and tris (dibenzylidene-BASE acetone) dipalladium into an organic solvent, cooling to room temperature after a catalyst is combined with a ligand, adding 2, 5-dichloroterephthalonitrile, benzophenone imine and sodium tert-butoxide, carrying out reflux reaction, and then separating and purifying to obtain 2, 5-bis ((diphenylmethylene) amino) terephthalonitrile;
a2) dissolving 2, 5-bis ((diphenylmethylene) amino) terephthalonitrile in tetrahydrofuran, adding hydrochloric acid water solution, carrying out reduction reaction, and separating and purifying to obtain 1, 4-diamino-2, 5-dicyanobenzene hydrochloride;
a3) adding 1, 4-diamino-2, 5-dicyanobenzene hydrochloride into an aqueous solution of sodium hydroxide, performing neutralization reaction, and separating and purifying to obtain the 1, 4-diamino-2, 5-dicyanobenzene;
the chemical reaction formula of the preparation process is as follows:
6. the method for preparing trimeric quinazoline knotted two-dimensional covalent organic framework material of claim 5,
in the step a 1), the separation and purification is to cool the mixture to room temperature after the reflux reaction is finished, and then to obtain 2, 5-bis ((diphenylmethylene) amino) terephthalonitrile through column chromatography purification;
in the step a 2), the separation and purification is to concentrate and remove the solvent after the reduction reaction is finished to obtain a crude product of 1, 4-diamino-2, 5-dicyanobenzene hydrochloride, wash the crude product with n-hexane, filter and dry the crude product to obtain the 1, 4-diamino-2, 5-dicyanobenzene hydrochloride;
in the step a 3), the separation and purification includes adding ethyl acetate for extraction after the neutralization reaction is finished, separating phases, drying the obtained ethyl acetate phase through anhydrous sodium sulfate, filtering, concentrating to remove the solvent, and drying to obtain the 1, 4-diamino-2, 5-dicyanobenzene.
7. The method for preparing a trimeric quinazoline-bonded two-dimensional covalent organic framework material according to claim 6, wherein in the step a 1), the eluent for the column chromatography is a mixture of 1: 0.5-6 of a mixed solution of ethyl acetate and petroleum ether.
8. The method for preparing trimeric quinazoline knotted two-dimensional covalent organic framework material of claim 5,
in the step a 1), the temperature for combining the catalyst and the ligand is 40-120 ℃, and the time is 1.5-3 h;
the time of the reflux reaction is 36-72 h;
in the step a 2), the temperature of the reduction reaction is 20-50 ℃ and the time is 8-20 h;
in the step a 3), the temperature of the neutralization reaction is 0-50 ℃ and the time is 0.5-3 h.
9. The method for preparing trimeric quinazoline knotted two-dimensional covalent organic framework material of claim 5,
in the step a 1), the organic solvent is toluene, ethyl acetate or dichloromethane;
the molar ratio of (+ -) -2,2 '-bis (diphenylphosphino) -1, 1' -binaphthyl to tris (dibenzylidene-BASE acetone) dipalladium is 1: 0.25 to 1;
the weight ratio of the 2, 5-dichloro-terephthalonitrile, the benzophenone imine and the sodium tert-butoxide is 1: 1-4: 1-6;
the weight volume ratio of the 2, 5-dichloro-terephthalonitrile to the organic solvent is 1 kg: 15-65L;
in step a 2), the weight to volume ratio of 2, 5-bis ((diphenylmethylene) amino) terephthalonitrile to tetrahydrofuran was 1 kg: 20-50L;
the concentration of the hydrochloric acid aqueous solution is 1-2 mol/L;
the molar ratio of the 2, 5-bis ((diphenylmethylene) amino) terephthalonitrile to the hydrochloric acid in the aqueous hydrochloric acid solution is 1: 2-4;
in the step a 3), the concentration of the sodium hydroxide aqueous solution is 0.5-1.2 mol/L;
the mol ratio of the 1, 4-diamino-2, 5-dicyanobenzene hydrochloride to the sodium hydroxide is 1:1 to 4.
10. The use of a trimeric quinazoline knotted two-dimensional covalent organic framework material as claimed in claim 1, wherein said nitrogen-containing conjugated microporous polymer network supports a molybdenum disulfide composite as an adsorbent for the adsorption of greenhouse gases; or as a catalyst for electrocatalytic hydrogen evolution reaction.
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