CN112538167A - Alkyl chain modified acylhydrazone bond-linked covalent organic framework material and application thereof in photocatalytic hydrogen peroxide production - Google Patents
Alkyl chain modified acylhydrazone bond-linked covalent organic framework material and application thereof in photocatalytic hydrogen peroxide production Download PDFInfo
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 title claims abstract description 40
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 title claims description 8
- 239000000126 substance Substances 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 51
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000000605 extraction Methods 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 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 description 9
- 239000011521 glass Substances 0.000 claims description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 8
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- RXFWPOMAJBVGRU-UHFFFAOYSA-N 4-[4,6-bis(4-formylphenyl)-1,3,5-triazin-2-yl]benzaldehyde Chemical compound N1=C(N=C(N=C1C1=CC=C(C=O)C=C1)C1=CC=C(C=O)C=C1)C1=CC=C(C=O)C=C1 RXFWPOMAJBVGRU-UHFFFAOYSA-N 0.000 claims description 5
- 238000010257 thawing Methods 0.000 claims description 5
- 238000011282 treatment Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 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 4
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- ANOOTOPTCJRUPK-UHFFFAOYSA-N 1-iodohexane Chemical compound CCCCCCI ANOOTOPTCJRUPK-UHFFFAOYSA-N 0.000 claims description 3
- UWLHSHAHTBJTBA-UHFFFAOYSA-N 1-iodooctane Chemical compound CCCCCCCCI UWLHSHAHTBJTBA-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- KMGBZBJJOKUPIA-NUTRPMROSA-N 1-iodobutane Chemical group CCC[11CH2]I KMGBZBJJOKUPIA-NUTRPMROSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 15
- 238000003786 synthesis reaction Methods 0.000 abstract description 14
- 238000002360 preparation method Methods 0.000 abstract description 13
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 6
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 238000004729 solvothermal method Methods 0.000 abstract description 2
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 abstract 2
- 230000000694 effects Effects 0.000 abstract 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 19
- 239000005297 pyrex Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- -1 2, 5-bis (butoxy) terephthaloyl hydrazine Chemical compound 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 238000002525 ultrasonication Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KKIMDKMETPPURN-UHFFFAOYSA-N 1-(3-(trifluoromethyl)phenyl)piperazine Chemical compound FC(F)(F)C1=CC=CC(N2CCNCC2)=C1 KKIMDKMETPPURN-UHFFFAOYSA-N 0.000 description 3
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 3
- 241000973497 Siphonognathus argyrophanes Species 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 238000013032 photocatalytic reaction Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005406 washing Methods 0.000 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 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- YZZQEKHIQORAMI-UHFFFAOYSA-N CCCCCCONC(C(C=C1)=CC=C1C(N)=O)=O Chemical compound CCCCCCONC(C(C=C1)=CC=C1C(N)=O)=O YZZQEKHIQORAMI-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/029—Preparation from hydrogen and oxygen
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention discloses a series of acylhydrazone bond-linked covalent organic framework materials modified by different alkane branched chains, a preparation method thereof and application thereof in photocatalytic hydrogen peroxide production, and belongs to the technical field of material preparation. According to the invention, the grafting of the alkane branched chains with different lengths is realized in DMF after 2,5 dihydroxy terephthalic acid is esterified, and the acylhydrazone bond-linked covalent organic framework material modified by the alkane branched chains with different lengths is prepared by a solvothermal method. The preparation method is simple, the synthesis period is short, the preparation cost is low, the preparation method is environment-friendly, the prepared covalent organic framework material with the alkane branched chains with different lengths has the advantages of large specific surface area, stable structure and good activity of producing hydrogen peroxide by photocatalysis, and does not need to be combined with other substances, thereby providing a new catalyst synthesis and design idea for the field of photocatalysis synthesis, having important research value and practical significance, and having wide application prospect in other fields.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a series of acylhydrazone bond-linked covalent organic framework materials grafted with different alkane branched chains, a preparation method thereof and application thereof in the field of photocatalysis.
Background
Hydrogen peroxide (H)2O2) The reaction by-products are only water and oxygen, so the reaction by-products are green oxidants, and the green oxidants have wide application in various fields such as chemical industry, medical industry, printing and dyeing industry and the like. With the problem of energy shortage getting worse, people put more and more efforts into the research of renewable energy. Recently, researchers find that hydrogen peroxide can be used as a novel energy carrier, can be used as a fuel and an oxidant in a fuel cell at the same time, has high energy density, is convenient to store relative to hydrogen, and has wide application prospect in the field of single-chamber fuel cells. However, the traditional synthesis method has great disadvantages, which not only produces a large amount of organic by-products, but also has very high energy consumption. Another emerging method for directly generating hydrogen peroxide by hydrogen and oxygen under the action of a metal catalyst requires that the concentration of one of the gases is limited to a very small range to avoid explosion. The energy required for preparing hydrogen peroxide through the photocatalytic reaction is only illumination, the safety coefficient is high, and the method is very environment-friendly and is a very potential preparation method.
Covalent organic framework materials (COF), a class of organic nanomaterials emerging in recent years, have relatively light weight compared with other materials under the same volume condition due to their composition of light elements, and can be modified by exposed ordered groups due to their long-range order without worrying about the problems of non-uniform distribution of the modified materials. Covalent organic framework materials are linked by covalent bonds, which themselves are much more stable than other materials linked by ionic bonds with relatively low bond energies due to the high bond energies of the covalent bonds.
Disclosure of Invention
The invention provides a series of acylhydrazone bond-linked covalent organic framework materials grafted with alkane branched chains of different lengths and a preparation method thereof, and the acylhydrazone bond-linked covalent organic framework materials can realize effective photocatalytic production of hydrogen peroxide in an oxygen atmosphere.
In order to achieve the purpose, the invention adopts the following technical scheme:
an alkyl chain modified acylhydrazone bond-linked covalent organic framework material has a chemical structural formula as follows:
wherein R = - (CH)2)3-CH3、-(CH2)5-CH3、-(CH2)7-CH3。
The preparation method of the acylhydrazone bond-linked covalent organic framework material comprises the following steps:
(1) adding 2, 5-dihydroxy diethyl terephthalate into DMF, adding 1-iodoalkane and anhydrous potassium carbonate, stirring at room temperature for 12h, placing in a separating funnel, adding dichloromethane and saturated saline solution for extraction, taking the lower dichloromethane phase after liquid level layering, adding saturated saline solution again for extraction, repeatedly extracting for five times, and carrying out rotary evaporation on the obtained dichloromethane phase to obtain a product A;
(2) adding the product A obtained in the step (1) into ethanol, stirring, adding a hydrazine hydrate solution, reacting at 80 ℃ for 12 hours, naturally cooling, and performing suction filtration and cleaning treatment to obtain a product B;
(3) mixing the product B obtained in the step (2) with 2,4, 6-tri (4-aldehyde phenyl) -1,3, 5-triazine according to a certain proportion, placing the mixture in a glass tube, adding a mixed solution consisting of an acetic acid solution, mesitylene and 1, 4-dioxane, freezing in liquid nitrogen, vacuumizing to remove air, thawing, repeating the freezing, vacuumizing and thawing for four times, sealing the glass tube, placing the glass tube in an oven after cooling to room temperature, reacting at 90-120 ℃ for 48-72 hours, and performing suction filtration and cleaning on the product in the tube after cooling to room temperature to obtain the target product.
The molar ratio of diethyl 2, 5-dihydroxyterephthalate to 1-iodoalkane used in the step (1) is 1 (4-8), and the molar ratio of 1-iodoalkane to anhydrous potassium carbonate is 3: 5; the volume ratio of dichloromethane to saturated brine used was 4: 3. The 1-iodoalkane is 1-iodobutane, 1-iodohexane or 1-iodooctane.
The volume concentration of the hydrazine hydrate solution in the step (2) is 60-100%; the molar ratio of the product A to hydrazine hydrate is 1: 10-30.
The molar ratio of the product B used in the step (3) to the 2,4, 6-tris (4-formylphenyl) -1,3, 5-triazine is 3: 2.
The volume ratio of mesitylene, 1, 4-dioxane and acetic acid solution in the mixed solution in the step (3) is (13-15): (5-7): 2-4);
the concentration of the acetic acid solution is 3-6 mol/L.
The synthesized acylhydrazone bond-linked covalent organic framework material can effectively generate hydrogen peroxide in deionized water under the condition of light irradiation.
The two ligands in the covalent organic framework material provided by the invention are connected through hydrazone bonds, and compared with the traditional imine bond-connected covalent organic framework material, the hydrazone bonds have better stability and hydrolysis resistance, so that the application environment range of the covalent organic framework material is wider. The covalent organic framework material provided by the invention has a heterojunction structure due to the structural particularity of the material, and can realize generation and separation of electron-hole pairs under the illumination condition, so that the material can be used as a catalyst to perform photocatalytic reaction without loading any metal or other promoters, and the cost of the catalyst is effectively reduced.
The invention synthesizes the covalent organic framework material which has the alkane branched chains with different lengths and is connected through the hydrazone bond for the first time, and provides the characteristic that the covalent organic framework material has the characteristic of carrying out the photocatalytic synthesis of the hydrogen peroxide under the condition of no metal load for the first time, thereby providing another idea for the synthesis and the selection of the catalyst required by the photocatalytic synthesis of the hydrogen peroxide, enriching the selection and the design idea of the catalyst in the photocatalytic field, and providing a scheme with reference value for the subsequent research in the field.
The invention has the beneficial effects that:
1) the synthesized ligand and 2,4, 6-tri (4-aldehyde phenyl) -1,3, 5-triazine are used in a 1, 4-dioxane/mesitylene/acetic acid aqueous solution system to obtain a series of acylhydrazone bond-connected covalent organic framework materials with different alkane branch lengths by a solvothermal method, the obtained materials have large specific surface area, and the reduction reaction of oxygen can be realized under the oxygen atmosphere by illumination so as to generate hydrogen peroxide.
2) The synthetic method is simple and easy to implement, and the used reagents and raw materials are easy to obtain, so that the method has high industrial application value and is easy to popularize and apply.
Drawings
FIG. 1 is an X-ray powder diffraction contrast chart of DTT-COF obtained in example 1 and monomers used in the synthesis.
FIG. 2 is an X-ray powder diffraction contrast chart of BTH-COF obtained in example 2 and monomers used in the synthesis.
FIG. 3 is a graph of X-ray powder diffraction contrast of BOT-COF obtained in example 3 and monomers used in the synthesis.
FIG. 4 is a comparison graph of Fourier transform infrared spectra of DTT-COF obtained in example 1 and monomers used in the synthesis.
FIG. 5 is a comparison of Fourier transform infrared spectra of BTH-COF obtained in example 2 and monomers used in the synthesis.
FIG. 6 is a comparison of Fourier transform infrared spectra of BOT-COF obtained in example 3 and monomers used in the synthesis.
FIG. 7 shows N of DTT-COF obtained in example 12Adsorption-desorption isotherms.
FIG. 8 shows N in BTH-COF obtained in example 22Adsorption-desorption isotherms.
FIG. 9 shows N of BOT-COF obtained in example 32Adsorption-desorption isotherms.
FIG. 10 is a solid-state nuclear magnetic carbon spectrum of DTT-COF obtained in example 1.
FIG. 11 is a solid-state nuclear magnetic carbon spectrum of BTH-COF obtained in example 2.
FIG. 12 is a solid-state nuclear magnetic carbon spectrum of BOT-COF obtained in example 3.
FIG. 13 is a graph showing the relationship between the yield of hydrogen peroxide produced by photocatalytic reaction of DTT-COF, BTH-COF and BOT-COF in an oxygen atmosphere and time.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings, which are examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features mentioned in the embodiments of the present invention described below may be combined as long as they do not conflict with each other.
Example 1 preparation of DTT-COF
0.5g (1.97 mmol) of diethyl 2, 5-dihydroxyterephthalate is added to 10ml of DMF, 1.34ml (11.80 mmol) of 1-iodobutane and 2.716g (19.65 mmol) of anhydrous potassium carbonate are added, the mixture is stirred at room temperature for 12h and then placed in a separating funnel, 40ml of dichloromethane and saturated 30ml of saline are added for extraction, the lower dichloromethane phase is taken out after liquid level separation, 30ml of saturated saline is added again for extraction, after five times of extraction, the obtained dichloromethane phase is steamed by rotation, 0.5g (1.48 mmol) of the obtained product is taken and added to 5ml of ethanol for stirring, 1.5ml of 68% hydrazine hydrate (21 mmol) solution is added, the reaction is carried out at 80 ℃ for 12h and then is cooled naturally, and then the treatments of suction filtration and washing are carried out, thus obtaining 0.498g of 2, 5-bis (butoxy) terephthaloyl hydrazine.
After grinding and mixing 10mg (0.03 mmol) of the synthesized 2, 5-bis (butoxy) terephthaloyl hydrazine and 7.69mg (0.02 mmol) of 2,4, 6-tris (4-formylphenyl) -1,3, 5-triazine (TFTP), the mixture was added to a Pyrex tube having a length of 20cm, a diameter of 1cm and a volume of about 5ml, 0.333ml of 1, 4-dioxane and 0.666ml of mesitylene were then added, the tube mouth was sealed and subjected to ultrasonication for half an hour, then 0.2ml of a 3M acetic acid solution was added to the tube, the tube mouth was again subjected to ultrasonication for five minutes after sealing the tube mouth, then the Pyrex tube was placed in liquid nitrogen, gas in the tube was removed by vacuum evacuation after the liquid was completely frozen, then the solvent was thawed after closing the extraction valve, and the above freeze-vacuum-thaw operation was repeated 4 times to remove the ligand and gas present in the solvent. Then, the solvent in the Pyrex tube is frozen again by using liquid nitrogen, the Pyrex tube is thoroughly sealed by using a flame spray gun under the condition of vacuum pumping, the Pyrex tube is placed in a drying oven after the temperature is reduced to normal temperature under the condition of room temperature, the heating rate of the drying oven is controlled to be 1 ℃/min, the cooling rate is controlled to be 0.67 ℃/min, the maximum temperature is 120 ℃, the constant temperature is kept for 3 days under the condition of 120 ℃, the Pyrex tube is taken out when the temperature of the drying oven is reduced to room temperature according to a set program, solid products in a collecting tube are filtered, filtered and cleaned for four times by using acetone and tetrahydrofuran respectively, then the solid products are placed in a vacuum drying oven to be dried for 12 hours at the temperature of 60 ℃, and finally the butyl-modified acylhydrazone bond linked covalent organic frame is obtained and is marked as DTT-COF.
Example 2 preparation of BTH-COF
Adding 0.5g (1.97 mmol) of 2, 5-dihydroxy diethyl terephthalate into 10ml of DMF, adding 1.75ml (11.86 mmol) of 1-iodohexane and 2.716g (19.65 mmol) of anhydrous potassium carbonate, stirring at room temperature for 12h, placing the mixture into a separating funnel, adding 40ml of dichloromethane and saturated 30ml of saline solution for extraction, taking the lower dichloromethane phase after liquid level separation, adding 30ml of saturated saline solution again for extraction, repeating the extraction for five times, carrying out rotary evaporation on the obtained dichloromethane phase, taking 0.5g (1.37 mmol) of the obtained product, adding 1.5ml of hydrazine hydrate (21 mmol) solution with concentration of 68%, reacting at 80 ℃ for 12h, naturally cooling, carrying out suction filtration and washing treatment, and obtaining 0.498g of 2, 5-bis (hexyloxy) terephthaloyl hydrazine.
After grinding and mixing 10mg (0.024 mmol) of the synthesized 2, 5-bis (hexyloxy) terephthalamide with 6.60mg (0.016 mmol) of 2,4, 6-tris (4-formylphenyl) -1,3, 5-triazine (TFTP), was added to a Pyrex tube 20cm in length, 1cm in diameter and about 5ml in volume, 0.273ml of 1, 4-dioxane and 0.818ml of mesitylene were then added, the tube orifice was sealed and sonicated for half an hour, then 0.109ml of a 3M acetic acid solution was added to the tube, the tube orifice was sealed again and sonicated for five minutes, the Pyrex tube was placed in liquid nitrogen, after the liquid was completely frozen, the tube was evacuated to remove the gas, then the solvent was thawed after closing the suction valve, and the freeze-evacuate-thaw operation described above was repeated 4 times to remove the ligand and the gas present in the solvent. Then, the solvent in the Pyrex tube is frozen again by using liquid nitrogen, the Pyrex tube is thoroughly sealed by using a flame spray gun under the condition of vacuumizing, then the Pyrex tube is placed in a drying oven after the temperature is reduced to normal temperature under the condition of room temperature, the heating rate of the drying oven is controlled to be 1 ℃/min, the cooling rate is controlled to be 0.67 ℃/min, the maximum temperature is 120 ℃, the constant temperature is kept for 3 days under the condition of ensuring that the temperature is 120 ℃, the Pyrex tube is taken out when the temperature of the drying oven is reduced to room temperature according to a set program, solid products in a collecting tube are filtered, are respectively washed for four times by using acetone and tetrahydrofuran, then are placed in a vacuum drying oven to be dried for 12 hours at the temperature of 60 ℃, and finally the hexyl-modified acylhydrazone bond-linked covalent organic frame is obtained and is marked as BTH-.
Example 3 preparation of BOT-COF
Adding 0.5g (1.97 mmol) of 2, 5-dihydroxyterephthalic acid diethyl ester into 10ml of DMF, adding 2.15ml (11.84 mmol) of 1-iodooctane and 2.716g (19.65 mmol) of anhydrous potassium carbonate, stirring at room temperature for 12h, placing the mixture into a separating funnel, adding 40ml of dichloromethane and saturated 30ml of saline solution for extraction, taking the lower dichloromethane phase after liquid level separation, adding 30ml of saturated saline solution again for extraction, repeating the extraction for five times, carrying out rotary evaporation on the obtained dichloromethane phase, taking 0.5g (1.27 mmol) of the obtained product, adding 1.5ml of hydrazine hydrate (21 mmol) solution with the concentration of 68%, reacting at the temperature of 80 ℃ for 12h, naturally cooling, carrying out suction filtration and washing treatment, and obtaining 0.62g of 2, 5-bis (octyloxy) terephthaloyl hydrazine.
After grinding and mixing 10mg (0.021 mmol) of the synthesized 2, 5-bis (octyloxy) terephthaloyl hydrazine and 5.78mg (0.014 mmol) of 2,4, 6-tris (4-formylphenyl) -1,3, 5-triazine (TFTP), the mixture was added to a Pyrex tube having a length of 20cm, a diameter of 1cm and a volume of about 5ml, 0.250ml of 1, 4-dioxane and 0.750ml of mesitylene were then added, the tube opening was sealed and subjected to ultrasonication for half an hour, then 0.2ml of 6M acetic acid solution was added to the tube, the tube opening was sealed again and subjected to ultrasonication for five minutes, then the Pyrex tube was placed in liquid nitrogen, after the liquid was completely frozen, gas in the tube was removed by evacuation, then the solvent was thawed after the suction valve was closed, and the above freezing-evacuation-thawing operation was repeated 4 times to remove the ligand and the gas present in the solvent. Then, the solvent in the Pyrex tube is frozen again by using liquid nitrogen, the Pyrex tube is thoroughly sealed by using a flame spray gun under the condition of vacuum pumping, the Pyrex tube is placed in a drying oven after the temperature is reduced to normal temperature under the condition of room temperature, the heating rate of the drying oven is controlled to be 1 ℃/min, the cooling rate is controlled to be 0.67 ℃/min, the maximum temperature is 120 ℃, the constant temperature is kept for 3 days under the condition of 120 ℃, the Pyrex tube is taken out when the temperature of the drying oven is reduced to room temperature according to a set program, solid products in a collecting tube are filtered, are respectively washed for four times by using acetone and tetrahydrofuran, then are placed in a vacuum drying oven to be dried for 12 hours at the temperature of 60 ℃, and finally the octyl-modified acylhydrazone bond covalent organic frame is obtained and is labeled as BOT-COF.
FIGS. 1, 2 and 3 are X-ray powder diffraction contrast charts of the alkyl chain modified acylhydrazone bond-linked covalent organic framework material and the monomers used for synthesis obtained in examples 1 to 3, respectively. The reaction proceeded smoothly as evidenced by the change in the characteristic peaks of the monomer and product in the figure, and the product had a crystal structure.
FIGS. 4, 5 and 6 are Fourier transform infrared spectroscopy comparison graphs of the alkyl chain modified acylhydrazone bond-linked covalent organic framework material obtained in examples 1 to 3 and the monomers used for synthesis, respectively. The formation of hydrazone bonds is evidenced by the presence of characteristic peaks corresponding to carbon-nitrogen double bonds in the product in the figure.
FIGS. 7, 8 and 9 are N-bonds of the alkyl chain modified acylhydrazone bond-linked covalent organic framework materials obtained in examples 1 to 3, respectively2Adsorption-desorption isotherms.
FIGS. 10, 11, and 12 are solid-state nuclear magnetic carbon spectrograms of the alkyl chain modified acylhydrazone bond-linked covalent organic framework materials obtained in examples 1-3, respectively. The length of the branched chain contained in the product is proved by the characteristic peaks corresponding to the alkyl chain carbon atoms existing in the figure (in fig. 12, the number of the characteristic peaks is less than that of the alkyl chain carbon atoms due to the superposition of partial characteristic peaks).
Application examples
10mg of the target product obtained in the embodiment 1-3 is respectively added into a Pyrex glass bottle, then 50ml of deionized water is added, the opening is sealed by a rubber plug and then ultrasonic treatment is carried out for 30min, then oxygen is introduced into the water through a needle head, the pressure in the bottle is kept balanced, the oxygen introduction time is 30mim, and the oxygen atmosphere in the glass bottle is ensured by introducing an oxygen balloon. And then irradiating the glass bottle by using a xenon lamp with an optical filter of 420nm, sampling 0.5ml through a needle head every other hour, filtering, mixing the filtered liquid with 2ml of cerium sulfate solution, slightly shaking the mixture under the dark condition, standing the mixture for 30min, measuring the peak of the solution by using the ultraviolet light of the liquid, comparing the peak with a cerium sulfate standard solution, and calculating the amount of generated hydrogen peroxide according to the corresponding relation between the peak and the concentration and the reaction proportion of a chemical reaction equation. The results are shown in FIG. 13.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (8)
1. An alkyl chain modified acylhydrazone bond-linked covalent organic framework material is characterized in that the chemical structural formula is as follows:
wherein R = - (CH)2)3-CH3、-(CH2)5-CH3、-(CH2)7-CH3。
2. A method of preparing the acylhydrazone-linked covalent organic framework material of claim 1, comprising the steps of:
(1) adding 2, 5-dihydroxy diethyl terephthalate into DMF, adding 1-iodoalkane and anhydrous potassium carbonate, stirring at room temperature for 12h, placing in a separating funnel, adding dichloromethane and saturated saline solution for extraction, taking the lower dichloromethane phase after liquid level layering, adding saturated saline solution again for extraction, repeatedly extracting for five times, and carrying out rotary evaporation on the obtained dichloromethane phase to obtain a product A;
(2) adding the product A obtained in the step (1) into ethanol, stirring, adding a hydrazine hydrate solution, reacting at 80 ℃ for 12 hours, naturally cooling, and performing suction filtration and cleaning treatment to obtain a product B;
(3) mixing the product B obtained in the step (2) with 2,4, 6-tri (4-aldehyde phenyl) -1,3, 5-triazine according to a certain proportion, placing the mixture in a glass tube, adding a mixed solution consisting of an acetic acid solution, mesitylene and 1, 4-dioxane, freezing in liquid nitrogen, vacuumizing to remove air, thawing, repeating the freezing, vacuumizing and thawing for four times, sealing the glass tube, placing the glass tube in an oven after cooling to room temperature, reacting at 90-120 ℃ for 48-72 hours, and performing suction filtration and cleaning on the product in the tube after cooling to room temperature to obtain the target product.
3. The method of preparing an acylhydrazone-linked covalent organic framework material of claim 2, wherein: the molar ratio of diethyl 2, 5-dihydroxyterephthalate to 1-iodoalkane used in the step (1) is 1 (4-8), and the molar ratio of 1-iodoalkane to anhydrous potassium carbonate is 3: 5;
the 1-iodoalkane is 1-iodobutane, 1-iodohexane or 1-iodooctane.
4. The method of preparing an acylhydrazone-linked covalent organic framework material of claim 2, wherein: the volume ratio of the dichloromethane to the saturated saline solution used in the step (1) is 4: 3.
5. The method of preparing an acylhydrazone-linked covalent organic framework material of claim 2, wherein: the volume concentration of the hydrazine hydrate solution in the step (2) is 60-100%; the molar ratio of the product A to hydrazine hydrate is 1: 10-30.
6. The method of preparing an acylhydrazone-linked covalent organic framework material of claim 2, wherein: the molar ratio of the product B used in the step (3) to the 2,4, 6-tris (4-formylphenyl) -1,3, 5-triazine is 3: 2.
7. The method of preparing an acylhydrazone-linked covalent organic framework material of claim 2, wherein: the volume ratio of mesitylene, 1, 4-dioxane and acetic acid solution in the mixed solution in the step (3) is (13-15): (5-7): 2-4);
the concentration of the acetic acid solution is 3-6 mol/L.
8. Use of the acylhydrazone bond-linked covalent organic framework material of claim 1 in the photocatalytic production of hydrogen peroxide.
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