CN112625200A - Covalent organic framework material and preparation method thereof - Google Patents
Covalent organic framework material and preparation method thereof Download PDFInfo
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- CN112625200A CN112625200A CN202011393265.4A CN202011393265A CN112625200A CN 112625200 A CN112625200 A CN 112625200A CN 202011393265 A CN202011393265 A CN 202011393265A CN 112625200 A CN112625200 A CN 112625200A
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 101
- 239000000463 material Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- 238000010438 heat treatment Methods 0.000 claims abstract description 42
- 238000001816 cooling Methods 0.000 claims abstract description 39
- 238000004321 preservation Methods 0.000 claims abstract description 34
- -1 rare earth compound Chemical class 0.000 claims abstract description 34
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 32
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011858 nanopowder Substances 0.000 claims abstract description 22
- 239000012065 filter cake Substances 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 20
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 16
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 16
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 16
- QHQSCKLPDVSEBJ-UHFFFAOYSA-N 1,3,5-tri(4-aminophenyl)benzene Chemical compound C1=CC(N)=CC=C1C1=CC(C=2C=CC(N)=CC=2)=CC(C=2C=CC(N)=CC=2)=C1 QHQSCKLPDVSEBJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 11
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims abstract description 11
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 10
- 238000007599 discharging Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 150000003459 sulfonic acid esters Chemical class 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000007789 sealing Methods 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 15
- WJUFSDZVCOTFON-UHFFFAOYSA-N veratraldehyde Chemical compound COC1=CC=C(C=O)C=C1OC WJUFSDZVCOTFON-UHFFFAOYSA-N 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- UQOUOXLHXPHDHF-UHFFFAOYSA-N diethyl 2,5-dihydroxybenzene-1,4-dicarboxylate Chemical compound CCOC(=O)C1=CC(O)=C(C(=O)OCC)C=C1O UQOUOXLHXPHDHF-UHFFFAOYSA-N 0.000 claims description 10
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 8
- BIFWGDWGCZLCHF-UHFFFAOYSA-N 4-bromo-2,5-dimethoxybenzaldehyde Chemical compound COC1=CC(C=O)=C(OC)C=C1Br BIFWGDWGCZLCHF-UHFFFAOYSA-N 0.000 claims description 7
- GERYZUPKZWOWMJ-UHFFFAOYSA-N COC1(C(C=C(C=C1)OC)C=O)C=O Chemical compound COC1(C(C=C(C=C1)OC)C=O)C=O GERYZUPKZWOWMJ-UHFFFAOYSA-N 0.000 claims description 7
- HPEVJTNZYIMANV-JTQLQIEISA-N [(2s)-2-methylbutyl] 4-methylbenzenesulfonate Chemical compound CC[C@H](C)COS(=O)(=O)C1=CC=C(C)C=C1 HPEVJTNZYIMANV-JTQLQIEISA-N 0.000 claims description 7
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 6
- MAYVZUQEFSJDHA-UHFFFAOYSA-N 1,5-bis(methylsulfanyl)naphthalene Chemical compound C1=CC=C2C(SC)=CC=CC2=C1SC MAYVZUQEFSJDHA-UHFFFAOYSA-N 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003990 capacitor Substances 0.000 claims description 6
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 6
- FLWXWKDFOLALOB-UHFFFAOYSA-H dysprosium(3+);trisulfate Chemical compound [Dy+3].[Dy+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FLWXWKDFOLALOB-UHFFFAOYSA-H 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- MSSJRSIYTDCKIR-DDWIOCJRSA-N CC=1C(=CC=CC1)S(=O)(=O)O.C1(=CC=CC=C1)[C@@H](CO)O Chemical compound CC=1C(=CC=CC1)S(=O)(=O)O.C1(=CC=CC=C1)[C@@H](CO)O MSSJRSIYTDCKIR-DDWIOCJRSA-N 0.000 claims description 4
- AGADOLNBSCBALT-VWMHFEHESA-N (5s)-5-(hydroxymethyl)pyrrolidin-2-one;4-methylbenzenesulfonic acid Chemical compound OC[C@@H]1CCC(=O)N1.CC1=CC=C(S(O)(=O)=O)C=C1 AGADOLNBSCBALT-VWMHFEHESA-N 0.000 claims description 3
- QXPQVUQBEBHHQP-UHFFFAOYSA-N 5,6,7,8-tetrahydro-[1]benzothiolo[2,3-d]pyrimidin-4-amine Chemical compound C1CCCC2=C1SC1=C2C(N)=NC=N1 QXPQVUQBEBHHQP-UHFFFAOYSA-N 0.000 claims description 3
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- ONIHPYYWNBVMID-UHFFFAOYSA-N diethyl benzene-1,4-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)C=C1 ONIHPYYWNBVMID-UHFFFAOYSA-N 0.000 abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 50
- 230000000052 comparative effect Effects 0.000 description 13
- 238000000926 separation method Methods 0.000 description 11
- 239000013384 organic framework Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- RNVYQYLELCKWAN-YFKPBYRVSA-N [(4s)-2,2-dimethyl-1,3-dioxolan-4-yl]methanol Chemical compound CC1(C)OC[C@H](CO)O1 RNVYQYLELCKWAN-YFKPBYRVSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 239000005946 Cypermethrin Substances 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 239000005868 Metconazole Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002045 capillary electrochromatography Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- KAATUXNTWXVJKI-UHFFFAOYSA-N cypermethrin Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(=O)OC(C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 KAATUXNTWXVJKI-UHFFFAOYSA-N 0.000 description 1
- 229960005424 cypermethrin Drugs 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 239000013497 imine-linked covalent-organic framework Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- XWPZUHJBOLQNMN-UHFFFAOYSA-N metconazole Chemical compound C1=NC=NN1CC1(O)C(C)(C)CCC1CC1=CC=C(Cl)C=C1 XWPZUHJBOLQNMN-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000011800 void material Substances 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
-
- 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
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
-
- 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
- C08G12/40—Chemically modified polycondensates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
- B01J2220/52—Sorbents specially adapted for preparative chromatography
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
- B01J2220/54—Sorbents specially adapted for analytical or investigative chromatography
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/80—Aspects related to sorbents specially adapted for preparative, analytical or investigative chromatography
Abstract
The invention discloses a preparation method of a covalent organic framework material, which comprises the following steps: (1) mixing a rare earth compound, hydrotalcite and water, heating and then carrying out heat preservation reaction; then cooling to room temperature, discharging, filtering and washing the reaction solution, roasting a filter cake, and grinding to obtain rare earth ion modified hydrotalcite nano powder; (2) stirring and dispersing an organic solvent and the rare earth ion modified hydrotalcite nano powder prepared in the step (1), adding an aldehyde substance and 1,3, 5-tri (4-aminophenyl) benzene, heating and then carrying out heat preservation reaction; cooling to room temperature; (3) adding sulfonic acid ester, 2, 5-dihydroxy diethyl terephthalate and benzaldehyde, heating and then carrying out heat preservation reaction; cooling to room temperature; (4) adding 1,3, 5-benzene trimethyl aldehyde, 1, 4-dioxane and hydrazine hydrate, heating and then carrying out heat preservation reaction; cooling to room temperature; filtering, washing with organic solvent, and drying the filter cake. The covalent organic framework material has high specific surface area, high specific area capacity and high selective separability.
Description
Technical Field
The invention belongs to the technical field of covalent organic framework materials, and particularly relates to a covalent organic framework material and a preparation method thereof.
Background
Covalent organic framework materials (COFs) are two-or three-dimensional organic porous materials connected by Covalent bonds. The COFs can obtain rich functional materials by designing reaction precursors and reaction types with different geometric structures, and the porous two-dimensional or three-dimensional COFs material has the characteristics of low density (completely consisting of light elements such as C, H, N, B, Si, O and the like), complete structure, high specific surface area, adjustable pore size and structure, more convenient functional modification and the like. The lattice unit cell formed by covalent bonds enables the material to have many advantages of good chemical stability, thermal stability and the like, so that the COFs material has potential application in various functional materials.
The COFs material has the characteristics of modifiable permanent nanometer holes or pore canals with adjustable size and structure, small density, high surface area, high thermal stability and the like; meanwhile, the two-dimensional COFs formed by rigid building monomers have a pi-pi stacked layered structure, and pi tracks between layers can generate larger electronic coupling to provide channels for carrier conduction. The advantages enable the COFs material to show excellent performance in the fields of clean energy hydrogen storage, photoelectric devices and catalysts. The high specific surface area, adjustable pore size and convenient functional modification of COFs materials are widely noticed and researched by scientists, people endow the covalent organic framework material with a specific function by designing various functional reaction precursors, and the covalent organic framework material has excellent performance in the fields of clean energy hydrogen storage, photoelectric devices and catalysts.
On the one hand, COFs materials have the advantages of lower density, structural integrity, high specific surface area, tunable and modifiable pores, high chemical and thermal stability. In view of the requirements of electrode materials for high specific surface area, suitable void structure, capacity and balance of conductivity properties, COFs materials have the advantage of being exceptionally thick. Pseudocapacitive materials generally have a higher theoretical specific capacitance value, but actually exhibit a lower specific capacitance due to poor electrical conductivity. The COFs can be effectively applied to the industry of super capacitors as an organic pseudocapacitance material with excellent capacitance performance.
On the other hand, COFs are of particular interest as a novel class of porous crystalline organic polymers for applications in the field of analytical chemistry, such as chromatographic separations. At present, different types of COFs materials including β -ketoamine linked COFs, imine linked COFs, hydrazone linked COFs, and borate linked COFs have been successfully used as new stationary phases for gas chromatography or capillary electrochromatography. Thus, porous crystalline COFs can also be used effectively as good candidates for the separation of homologues, positional isomers and even enantiomeric compounds.
However, the current COFs materials have many key technical problems in preparation and application, which seriously affect the application in the fields of hydrogen storage materials, photoelectric materials, chiral separation, catalyst design and the like: (1) at present, the conventional preparation process of the COFs material is extremely complicated, the working procedure is complex, the yield is very low, and the production cost is extremely high. (2) The specific surface area and the conductivity of the COFs are poor, and the application of the COFs in the super capacitor industry is greatly limited. (3) If the COFs material is directly filled into the chromatographic column, the column efficiency of the chromatographic column is rapidly reduced due to the irregular size and shape of the COFs, and the like, so that the separation effect of the COFs material on compounds such as homologues and position isomers is seriously influenced. Therefore, how to prepare the COFs material with high specific surface area, high specific area capacity and high selective separability is a technical problem which is urgently solved by related industries at home and abroad at present.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a covalent organic framework material and a preparation method thereof, and the covalent organic framework material has high specific surface area, high specific area capacity and high selective separability.
The technical purpose of the invention is realized by the following technical scheme:
a method of preparing a covalent organic framework material, comprising the steps of:
(1) mixing the rare earth compound, the hydrotalcite and water, heating to 150-200 ℃ in a sealed manner, and reacting for 10-30min under the condition of heat preservation; then cooling to room temperature, discharging, filtering and washing the reaction solution, roasting the filter cake at 200-300 ℃ for 30-60min, and grinding to obtain rare earth ion modified hydrotalcite nano powder;
(2) stirring and dispersing an organic solvent and the rare earth ion modified hydrotalcite nano powder prepared in the step (1), adding an aldehyde substance and 1,3, 5-tri (4-aminophenyl) benzene, heating to 60-90 ℃ in a closed manner, and reacting for 3-6 hours in a heat preservation manner; after the reaction is finished, cooling to room temperature;
(3) adding sulfonic acid ester, diethyl 2, 5-dihydroxyterephthalate and benzaldehyde, sealing and heating to 60-90 ℃, and keeping the temperature for reaction for 3-6 h; after the reaction is finished, cooling to room temperature;
(4) adding 1,3, 5-benzenetricarboxylic acid, 1, 4-dioxane and hydrazine hydrate, heating to 60-90 ℃ in a closed manner, and reacting for 10-15 hours while keeping the temperature; after the reaction is finished, cooling to room temperature; filtering and washing with organic solvent, and drying the filter cake at the temperature of 120-150 ℃ to obtain the covalent organic framework material.
Preferably, the rare earth compound is at least one of cerium nitrate, cerium sulfate, cerium chloride, dysprosium nitrate, dysprosium sulfate and dysprosium chloride. The rare earth compound is used for doping modification of hydrotalcite, and only rare earth ion modified hydrotalcite can guide hydrazone bonds and imine bonds to grow along the front side and the side face of the hydrotalcite.
Preferably, the organic solvent is at least one of o-dichlorobenzene, mesitylene, methanol, ethanol, n-butanol, acetone, butanone, tetrahydrofuran and pyridine.
Preferably, the aldehyde is at least one of 2, 5-dimethoxybenzene dicarbaldehyde, 3, 4-dimethoxybenzaldehyde, and 4-bromo-2, 5-dimethoxybenzaldehyde. The aldehyde substance has the function of gradually generating an imine COFs system along the side surface of the hydrotalcite under the guidance of the rare earth ion modified hydrotalcite and 1,3, 5-tri (4-aminophenyl) benzene by a solvothermal method; the system imparts a high area specific capacity to the material, and thus can be used as a supercapacitor.
Preferably, the sulfonic acid ester is at least one of (S) -2-methylbutyl-4-methylbenzenesulfonate, (S) - (+) -2, 2-dimethyl-1, 3-dioxocyclopentyl-4-methanol-p-methylbenzenesulfonate, (S) -2-methylbutyl-p-toluenesulfonate, (S) - (+) -binaphthol-p-toluenesulfonate, (S) - (+) -1-phenyl-1, 2-ethanediol-2-toluenesulfonate, and (S) - (+) -5-hydroxymethyl-2-pyrrolidone-p-toluenesulfonate. Under the guide of the rare earth ion modified hydrotalcite, the sulfonate reacts with 2, 5-dihydroxy diethyl terephthalate and benzaldehyde along the side surface of the hydrotalcite to generate a model compound, and then the model compound reacts with 1,3, 5-benzenetricarboxylic aldehyde, 1, 4-dioxane and hydrazine hydrate to generate a hydrazone bond connected chiral COFs system; the system endows the material with high selectivity separation, thereby being applicable to separation of substances such as homologues.
Preferably, the method comprises the following detailed steps:
(1) firstly, adding 1-5 parts of rare earth compound and 10-20 parts of hydrotalcite into 90-110 parts of water in a hydrothermal reaction kettle, then raising the temperature to 150 ℃ and 200 ℃ in a closed manner, and carrying out heat preservation reaction for 10-30 min; stopping the reaction, cooling to room temperature, discharging, filtering the reaction solution, fully washing, roasting the filter cake at 200-300 ℃ for 30-60min, and fully grinding to obtain the rare earth ion modified hydrotalcite nano powder;
(2) secondly, adding 320 parts of 280 plus organic solvent into a hydrothermal reaction kettle, adding 0.1-0.5 part of the rare earth ion modified hydrotalcite nano powder prepared in the step (1), fully stirring and dispersing, then adding 30-50 parts of aldehyde substance and 10-30 parts of 1,3, 5-tri (4-aminophenyl) benzene, then sealing and heating to 60-90 ℃, and carrying out heat preservation reaction for 3-6 hours; after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature;
(3) adding 20-40 parts of sulfonic acid ester, 3-7 parts of diethyl 2, 5-dihydroxyterephthalate and 8-15 parts of benzaldehyde into a hydrothermal reaction kettle, then sealing and heating to 60-90 ℃, and carrying out heat preservation reaction for 3-6 hours; after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature;
(4) adding 9-12 parts of 1,3, 5-benzenetricarboxylic acid, 12-17 parts of 1, 4-dioxane and 3-8 parts of hydrazine hydrate into a hydrothermal reaction kettle, then sealing and heating to 60-90 ℃, and carrying out heat preservation reaction for 10-15 h; after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature; then filtering and fully washing by using an organic solvent, and finally drying the filter cake at the temperature of 120-150 ℃ in vacuum to constant weight to obtain the covalent organic framework material.
In the preparation process of the covalent organic framework material, the rare earth ion modified hydrotalcite nano powder prepared in the step (1) needs to react with aldehyde substances and 1,3, 5-tri (4-aminophenyl) benzene in an organic solvent in a closed heating manner, and then reacts with sulfonic acid ester, diethyl 2, 5-dihydroxyterephthalate and benzaldehyde in a closed heating manner, so that the performance of the finally prepared covalent organic framework material can be ensured, and meanwhile, the high-temperature hydrothermal reaction parameters and the roasting conditions do not accord with the conditions defined by the invention, and the performance of the finally prepared covalent organic framework material can be influenced.
It is another object of the present invention to provide a covalent organic framework material as described above, which is prepared by the above preparation method.
Use of the above covalent organic framework materials in capacitor materials.
Use of the above covalent organic framework materials in chromatographic materials.
The invention has the beneficial effects that:
(1) the preparation process has the advantages of mild conditions, obviously lower reaction temperature, obviously shortened reaction time, simpler process, lower production cost, high operation safety coefficient and high yield of the target product.
(2) In the structure of the COFs material prepared by the invention, on one hand, the side surface of the hydrotalcite is provided with a mature imine COFs system, and the system enables the COFs material to have large specific surface area, good and balanced conductivity and excellent impedance performance, so that the COFs material can be used as a super capacitor. On the other hand, the front surface of the hydrotalcite has a mature hydrazone bond COFs chiral system, and the system enables the COFs material to have an excellent selective separation effect. The prepared COFs material has quite regular microscopic size and shape and convergent orientation (mainly distributed along the water slide front), and is filled into chromatographic columns such as HPLC (high performance liquid chromatography) and the like, so that the chromatographic column has excellent column effect and good separation effect.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1:
a method of preparing a covalent organic framework material, comprising the steps of:
(1) firstly, adding 1 part of cerium nitrate and 10 parts of hydrotalcite into 100 parts of water in a hydrothermal reaction kettle, then sealing and heating to 150 ℃, and carrying out heat preservation reaction for 10 min; stopping the reaction, cooling to room temperature, discharging, filtering the reaction solution, fully washing, roasting a filter cake at 200 ℃ for 30min, and fully grinding to obtain rare earth ion modified hydrotalcite nano powder;
(2) secondly, adding 300 parts of o-dichlorobenzene into a hydrothermal reaction kettle, adding 0.1 part of the rare earth ion modified hydrotalcite nano powder prepared in the step (1), fully stirring and dispersing, then adding 30 parts of 2, 5-dimethoxybenzene dicarbaldehyde and 10 parts of 1,3, 5-tris (4-aminophenyl) benzene, then sealing and heating to 60 ℃, and carrying out heat preservation reaction for 3 hours; after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature;
(3) adding 20 parts of (S) -2-methylbutyl-4-methylbenzenesulfonate, 5 parts of diethyl 2, 5-dihydroxyterephthalate and 10 parts of benzaldehyde into a hydrothermal reaction kettle, then sealing and heating to 60 ℃, and carrying out heat preservation reaction for 3 hours; after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature;
(4) adding 10 parts of 1,3, 5-benzenetricarboxylic acid, 15 parts of 1, 4-dioxane and 5 parts of hydrazine hydrate into a hydrothermal reaction kettle, then heating to 60 ℃ in a closed manner, and reacting for 10 hours in a heat preservation manner; after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature; then filtering and fully washing with ethanol, and finally drying the filter cake at 120 ℃ in vacuum to constant weight to obtain the covalent organic framework material which is marked as COFs 1.
Example 2:
a method of preparing a covalent organic framework material, comprising the steps of:
(1) firstly, adding 2.5 parts of cerium sulfate, 2.5 parts of dysprosium nitrate and 20 parts of hydrotalcite into 100 parts of water in a hydrothermal reaction kettle, then sealing and heating to 200 ℃, and carrying out heat preservation reaction for 30 min; stopping the reaction, cooling to room temperature, discharging, filtering the reaction solution, fully washing, roasting a filter cake at 300 ℃ for 60min, and fully grinding to obtain rare earth ion modified hydrotalcite nano powder;
(2) secondly, adding 150 parts of mesitylene and 150 parts of methanol into a hydrothermal reaction kettle, adding 0.5 part of the rare earth ion modified hydrotalcite nano powder prepared in the step (1), fully stirring and dispersing, then adding 25 parts of 3, 4-dimethoxybenzaldehyde, 25 parts of 4-bromo-2, 5-dimethoxybenzaldehyde and 30 parts of 1,3, 5-tri (4-aminophenyl) benzene, and then heating to 90 ℃ in a closed manner and reacting for 6 hours in a heat preservation manner; after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature;
(3) adding 20 parts of (S) - (+) -2, 2-dimethyl-1, 3-dioxolane-4-methanol p-methylbenzenesulfonate, 20 parts of (S) -2-methylbutyl p-toluenesulfonate, 5 parts of diethyl 2, 5-dihydroxyterephthalate and 10 parts of benzaldehyde into a hydrothermal reaction kettle, then heating to 90 ℃ in a closed manner, and carrying out heat preservation reaction for 6 hours; after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature;
(4) adding 10 parts of 1,3, 5-benzenetricarboxylic acid, 15 parts of 1, 4-dioxane and 5 parts of hydrazine hydrate into a hydrothermal reaction kettle, then heating to 90 ℃ in a closed manner, and carrying out heat preservation reaction for 15 hours; after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature; then filtering and fully washing with ethanol, and finally drying the filter cake at 150 ℃ in vacuum to constant weight to obtain the covalent organic framework material which is marked as COFs 2.
Example 3:
a method of preparing a covalent organic framework material, comprising the steps of:
(1) firstly, adding 1 part of cerium chloride, 1 part of dysprosium sulfate, 1 part of dysprosium chloride and 12 parts of hydrotalcite into 100 parts of water in a hydrothermal reaction kettle, then sealing and heating to 160 ℃, and carrying out heat preservation reaction for 15 min; stopping the reaction, cooling to room temperature, discharging, filtering the reaction solution, fully washing, roasting a filter cake at 210 ℃ for 40min, and fully grinding to obtain rare earth ion modified hydrotalcite nano powder;
(2) secondly, adding 100 parts of acetone, 100 parts of tetrahydrofuran and 100 parts of pyridine into a hydrothermal reaction kettle, adding 0.2 part of the rare earth ion modified hydrotalcite nano powder prepared in the step (1), fully stirring and dispersing, then adding 10 parts of 2, 5-dimethoxybenzene dicarbaldehyde, 15 parts of 3, 4-dimethoxybenzaldehyde, 10 parts of 4-bromo-2, 5-dimethoxybenzaldehyde and 15 parts of 1,3, 5-tri (4-aminophenyl) benzene, and then heating to 70 ℃ in a sealed manner and reacting for 4 hours in a heat preservation manner; after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature;
(3) adding 10 parts of (S) - (+) -binaphthol di-p-toluenesulfonate, 15 parts of (S) - (+) -1-phenyl-1, 2-glycol-2-toluenesulfonate, 5 parts of 2, 5-dihydroxyterephthalic acid diethyl ester and 10 parts of benzaldehyde into a hydrothermal reaction kettle, then sealing and heating to 70 ℃, and carrying out heat preservation reaction for 4 hours; after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature;
(4) adding 10 parts of 1,3, 5-benzenetricarboxylic acid, 15 parts of 1, 4-dioxane and 5 parts of hydrazine hydrate into a hydrothermal reaction kettle, then heating to 70 ℃ in a closed manner, and reacting for 12 hours in a heat preservation manner; after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature; then filtering and fully washing with ethanol, and finally drying the filter cake at 125 ℃ in vacuum to constant weight to obtain the covalent organic framework material which is marked as COFs 3.
Example 4:
a method of preparing a covalent organic framework material, comprising the steps of:
(1) firstly, adding 1 part of cerium nitrate, 1 part of cerium chloride, 1 part of dysprosium sulfate, 1 part of dysprosium chloride and 18 parts of hydrotalcite into 100 parts of water in a hydrothermal reaction kettle, then heating to 190 ℃ in a closed manner, and carrying out heat preservation reaction for 28 min; stopping the reaction, cooling to room temperature, discharging, filtering the reaction solution, fully washing, roasting a filter cake at 280 ℃ for 55min, and fully grinding to obtain rare earth ion modified hydrotalcite nano powder;
(2) adding 50 parts of ethanol, 100 parts of n-butanol, 100 parts of butanone and 50 parts of pyridine into a hydrothermal reaction kettle, adding 0.4 part of the rare earth ion modified hydrotalcite nano powder prepared in the step (1), fully stirring and dispersing, then adding 5 parts of 2, 5-dimethoxybenzene dicarbaldehyde, 20 parts of 3, 4-dimethoxybenzaldehyde, 20 parts of 4-bromo-2, 5-dimethoxybenzaldehyde and 15 parts of 1,3, 5-tri (4-aminophenyl) benzene, and then heating to 80 ℃ in a sealed manner and reacting for 5 hours with heat preservation; after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature;
(3) adding 5 parts of (S) - (+) -2, 2-dimethyl-1, 3-dioxolane-4-methanol p-methylbenzenesulfonate, 5 parts of (S) -2-methylbutyl p-toluenesulfonate, 15 parts of (S) - (+) -binaphthol di-p-toluenesulfonate, 5 parts of (S) - (+) -1-phenyl-1, 2-ethanediol-2-toluenesulfonate, 10 parts of (S) - (+) -5-hydroxymethyl-2-pyrrolidone p-toluenesulfonate, 5 parts of 2, 5-dihydroxyterephthalic acid diethyl ester and 10 parts of benzaldehyde into a hydrothermal reaction kettle, then sealing and heating to 80 ℃ and preserving heat for 5 hours; after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature;
(4) adding 10 parts of 1,3, 5-benzenetricarboxylic acid, 15 parts of 1, 4-dioxane and 5 parts of hydrazine hydrate into a hydrothermal reaction kettle, then sealing and heating to 80 ℃, and carrying out heat preservation reaction for 14 hours; after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature; then filtering and fully washing with ethanol, and finally drying the filter cake at 140 ℃ in vacuum to constant weight to obtain the covalent organic framework material which is marked as COFs 4.
Comparative example 1:
a method of preparing a covalent organic framework material, comprising the steps of:
(1) firstly, adding 1 part of cerium chloride, 1 part of dysprosium sulfate, 1 part of dysprosium chloride and 12 parts of hydrotalcite into 100 parts of water in a hydrothermal reaction kettle, then sealing and heating to 160 ℃, and carrying out heat preservation reaction for 15 min; stopping the reaction, cooling to room temperature, discharging, filtering the reaction solution, fully washing, roasting a filter cake at 210 ℃ for 40min, and fully grinding to obtain rare earth ion modified hydrotalcite nano powder;
(2) adding 0.2 part of the rare earth ion modified hydrotalcite nano powder prepared in the step (1), 10 parts of (S) - (+) -binaphthol di-p-toluenesulfonate, 15 parts of (S) - (+) -1-phenyl-1, 2-glycol-2-toluenesulfonate, 5 parts of 2, 5-dihydroxy diethyl terephthalate and 10 parts of benzaldehyde into a hydrothermal reaction kettle, fully stirring and dispersing, then heating to 70 ℃ in a sealed manner, and carrying out heat preservation reaction for 4 hours; after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature;
(3) adding 100 parts of acetone, 100 parts of tetrahydrofuran and 100 parts of pyridine into a hydrothermal reaction kettle, fully stirring and dispersing, then adding 10 parts of 2, 5-dimethoxybenzene dicarbaldehyde, 15 parts of 3, 4-dimethoxybenzaldehyde, 10 parts of 4-bromo-2, 5-dimethoxybenzaldehyde and 15 parts of 1,3, 5-tri (4-aminophenyl) benzene, and then heating to 70 ℃ in a closed manner and reacting for 4 hours in a heat preservation manner; after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature;
(4) adding 10 parts of 1,3, 5-benzenetricarboxylic acid, 15 parts of 1, 4-dioxane and 5 parts of hydrazine hydrate into a hydrothermal reaction kettle, then heating to 70 ℃ in a closed manner, and reacting for 12 hours in a heat preservation manner; after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature; then filtering and fully washing with ethanol, and finally drying the filter cake at 125 ℃ in vacuum to constant weight to obtain the covalent organic framework material which is marked as COFs 5.
Comparative example 2:
a method of preparing a covalent organic framework material, comprising the steps of:
(1) firstly, adding 1 part of cerium chloride, 1 part of dysprosium sulfate, 1 part of dysprosium chloride and 12 parts of hydrotalcite into 100 parts of water in a hydrothermal reaction kettle, then sealing and heating to 160 ℃, and carrying out heat preservation reaction for 15 min; stopping the reaction, cooling to room temperature, discharging, filtering the reaction solution, fully washing, roasting a filter cake at 210 ℃ for 40min, and fully grinding to obtain rare earth ion modified hydrotalcite nano powder;
(2) secondly, adding 100 parts of acetone, 100 parts of tetrahydrofuran and 100 parts of pyridine into a hydrothermal reaction kettle, then adding 0.2 part of the rare earth ion modified hydrotalcite nano powder prepared in the step (1), fully stirring and dispersing, then adding 10 parts of 2, 5-dimethoxybenzene dicarbaldehyde, 15 parts of 3, 4-dimethoxybenzaldehyde, 10 parts of 4-bromo-2, 5-dimethoxybenzaldehyde, 15 parts of 1,3, 5-tri (4-aminophenyl) benzene, 10 parts of (S) - (+) -binaphthol di-p-toluenesulfonate, 15 parts of (S) - (+) -1-phenyl-1, 2-ethanediol-2-toluenesulfonate, 5 parts of 2, 5-dihydroxyterephthalic acid diethyl ester and 10 parts of benzaldehyde, and then heating to 70 ℃ in a sealed manner and reacting for 4 hours under heat preservation; after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature;
(3) adding 10 parts of 1,3, 5-benzenetricarboxylic acid, 15 parts of 1, 4-dioxane and 5 parts of hydrazine hydrate into a hydrothermal reaction kettle, then heating to 70 ℃ in a closed manner, and reacting for 12 hours in a heat preservation manner; after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature; then filtering and fully washing with ethanol, and finally drying the filter cake at 125 ℃ in vacuum to constant weight to obtain the covalent organic framework material which is marked as COFs 6.
Comparative example 3:
the difference from example 3 is that the temperature after sealing and temperature rise in step (1) is 140 ℃, the rest steps and parameters are completely the same as example 3, and the prepared organic framework material is denoted as COFs 7.
Comparative example 4:
the difference from example 3 is that the temperature after sealing and temperature rise in step (1) is 205 ℃, the rest steps and parameters are completely the same as example 3, and the prepared organic framework material is denoted as COFs 8.
Comparative example 5:
the difference from example 3 is that the calcination temperature in step (1) is 190 ℃, the rest steps and parameters are identical to those of example 3, and the prepared organic framework material is denoted as COFs 9.
Comparative example 6:
the difference from example 3 is that the calcination temperature in step (1) is 310 ℃, the rest steps and parameters are identical to those of example 3, and the prepared organic framework material is denoted as COFs 10.
Comparative example 7:
the difference from example 3 is that the temperature after sealing and temperature rise in step (2) is 55 ℃, the remaining steps and parameters are exactly the same as those in example 3, and the organic framework material prepared is denoted as COFs 11.
Comparative example 8:
the difference from example 3 is that the temperature after sealing and temperature rise in step (2) is 95 ℃, the remaining steps and parameters are exactly the same as those in example 3, and the organic framework material prepared is denoted as COFs 12.
Comparative example 9:
the difference from example 3 is that the temperature after sealing and temperature rise in step (3) is 55 ℃, the remaining steps and parameters are exactly the same as those in example 3, and the organic framework material prepared is denoted as COFs 13.
Comparative example 10:
the difference from example 3 is that the temperature after sealing and temperature rise in step (3) is 95 ℃, the remaining steps and parameters are exactly the same as those in example 3, and the organic framework material prepared is denoted as COFs 14.
Comparative example 11:
the difference from example 3 is that the temperature after the sealing and temperature rise in step (4) is 55 ℃, the remaining steps and parameters are exactly the same as those in example 3, and the organic framework material prepared is denoted as COFs 15.
Comparative example 12:
the difference from example 3 is that the temperature after sealing and temperature rise in step (4) is 95 ℃, the remaining steps and parameters are exactly the same as those in example 3, and the organic framework material prepared is denoted as COFs 16.
Test examples
The covalent organic framework materials COFs1-COFs16 prepared in the above examples 1-4 and comparative examples 1-12, the import COFs material Sc-1x (Maxwell, USA) for super capacitor, and the import COFs material HCC-35 (Shimadzu, Japan) for high performance liquid chromatography were respectively subjected to capacitance performance test (current density in the test was 1 mA/cm)2) And separation effectiveness test (COFs materials were prepared into a desired slurry with methanol and then separately loaded into a stainless steel column liquid chromatography column at 8000 psi) with the results shown in table 1.
Table 1: results of Performance testing
As can be seen from the performance test results in Table 1, COFs1-COFs4 have high specific area capacity (at a current density of 1 mA/cm)2When the specific area capacity is up to 309.63mF/cm2And above) well aboveThe specific area capacity (the specific area capacity is only 137.28 mF/cm) of the imported like product Sc-1x2) The capacitance performance is far superior to that of imported like products. Meanwhile, the separation effect of COFs1-COFs4 on positional isomers (nitrotoluene and nitrochlorobenzene) is not less than 90%, the separation degree of cis-trans isomers (cypermethrin and metconazole) is close to 90%, and the chromatographic selective separation effect is very excellent and is remarkably superior to that of imported similar commodity HCC-35.
Comparing COFs3 and COFs5-COFs16 in Table 1, it can be seen that: in the preparation process of the covalent organic framework material, the rare earth ion modified hydrotalcite nano powder prepared in the step (1) needs to react with aldehyde substances and 1,3, 5-tri (4-aminophenyl) benzene in an organic solvent in a closed heating manner, and then reacts with sulfonic acid ester, diethyl 2, 5-dihydroxyterephthalate and benzaldehyde in a closed heating manner to ensure the performance of the finally prepared covalent organic framework material, for example, the performance of the finally prepared covalent organic framework material is poor due to the difference of preparation steps of COFs5-COFs6 in the preparation process, and meanwhile, the performance of the finally prepared covalent organic framework material is influenced because the high-temperature hydrothermal reaction parameters and the roasting conditions do not accord with the conditions defined by the invention, for example, the COFs7-COFs16 change the hydrothermal reaction parameters or the roasting temperature in the preparation process, all can degrade the performance of the final covalent organic framework material.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A method for preparing a covalent organic framework material, which is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing the rare earth compound, the hydrotalcite and water, heating to 150-200 ℃ in a sealed manner, and reacting for 10-30min under the condition of heat preservation; then cooling to room temperature, discharging, filtering and washing the reaction solution, roasting the filter cake at 200-300 ℃ for 30-60min, and grinding to obtain rare earth ion modified hydrotalcite nano powder;
(2) stirring and dispersing an organic solvent and the rare earth ion modified hydrotalcite nano powder prepared in the step (1), adding an aldehyde substance and 1,3, 5-tri (4-aminophenyl) benzene, heating to 60-90 ℃ in a closed manner, and reacting for 3-6 hours in a heat preservation manner; after the reaction is finished, cooling to room temperature;
(3) adding sulfonic acid ester, diethyl 2, 5-dihydroxyterephthalate and benzaldehyde, sealing and heating to 60-90 ℃, and keeping the temperature for reaction for 3-6 h; after the reaction is finished, cooling to room temperature;
(4) adding 1,3, 5-benzenetricarboxylic acid, 1, 4-dioxane and hydrazine hydrate, heating to 60-90 ℃ in a closed manner, and reacting for 10-15 hours while keeping the temperature; after the reaction is finished, cooling to room temperature; filtering and washing with organic solvent, and drying the filter cake at the temperature of 120-150 ℃ to obtain the covalent organic framework material.
2. The method of claim 1, wherein the covalent organic framework material is prepared by: the rare earth compound is at least one of cerium nitrate, cerium sulfate, cerium chloride, dysprosium nitrate, dysprosium sulfate and dysprosium chloride.
3. The method of claim 1, wherein the covalent organic framework material is prepared by: the organic solvent is at least one of o-dichlorobenzene, mesitylene, methanol, ethanol, n-butanol, acetone, butanone, tetrahydrofuran and pyridine.
4. The method of claim 1, wherein the covalent organic framework material is prepared by: the aldehyde substance is at least one of 2, 5-dimethoxy benzene dicarbaldehyde, 3, 4-dimethoxy benzaldehyde and 4-bromo-2, 5-dimethoxy benzaldehyde.
5. The method of claim 1, wherein the covalent organic framework material is prepared by: the sulfonate is at least one of (S) -2-methylbutyl-4-methylbenzenesulfonate, (S) - (+) -2, 2-dimethyl-1, 3-dioxocyclopentyl-4-methanol p-methylbenzenesulfonate, (S) -2-methylbutyl-p-toluenesulfonate, (S) - (+) -binaphthol-p-toluenesulfonate, (S) - (+) -1-phenyl-1, 2-ethanediol-2-toluenesulfonate, and (S) - (+) -5-hydroxymethyl-2-pyrrolidone p-toluenesulfonate.
6. A covalent organic framework material, characterized by: the covalent organic framework material is prepared according to the preparation method of any one of claims 1 to 5.
7. Use of the covalent organic framework material of claim 6 in capacitor materials.
8. Use of the covalent organic framework material of claim 6 in a chromatographic material.
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| CN115569639A (en) * | 2022-10-19 | 2023-01-06 | 西南医科大学 | Novel stationary phase high performance liquid chromatography packing of modified silica spheres and preparation method and application thereof |
| CN116272920A (en) * | 2023-03-10 | 2023-06-23 | 西南医科大学 | Triazine covalent organic framework modified silicon sphere novel stationary phase high performance liquid chromatography packing and preparation method and application thereof |
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