CN115028789A - Preparation and application of covalent organic framework material containing Salen group - Google Patents
Preparation and application of covalent organic framework material containing Salen group Download PDFInfo
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 33
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
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- 238000000034 method Methods 0.000 claims description 14
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- 239000000706 filtrate Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000012043 crude product Substances 0.000 claims description 10
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- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
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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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/063—Polymers comprising a characteristic microstructure
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- B01J35/39—
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
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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
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Abstract
The invention belongs to the field of covalent organic framework materials, and particularly relates to synthesis of a compound, a covalent organic framework material containing Salen units, and a preparation method and application thereof. The structural unit is a hexagonal crystal structure, and the cell parameter a is
b is
c is a
Alpha is 90 DEG,Beta is 90 degrees, and gamma is 120 degrees. Due to the uniqueness of the material structure, the material can be used as a photocatalyst, and can be directly subjected to gas-solid catalytic reaction under the drive of visible light to reduce carbon dioxide into carbon monoxide.
Description
Technical Field
The invention belongs to the field of covalent organic framework materials, and particularly relates to synthesis of a novel chemical compound, preparation of a covalent organic framework material containing a Salen structure and application of the covalent organic framework material in photocatalytic gas-solid carbon dioxide reduction.
Background
Human beings have long been highly dependent on fossil fuels as a primary source of energyWhereas fossil fuels are used in excess with a large emission of greenhouse gases, the greenhouse gas CO in the atmosphere in 2021 years 2 Has reached 417ppm (warning line is 350ppm), resulting in environmental problems seriously threatening the survival of human beings. Introducing CO 2 The cyclic utilization of the carbon resource converted into energy is the best way to solve the problems of energy shortage and environment. The 'artificial photosynthesis' technology is based on green plant photosynthesis as principle and uses solar energy as driving force to make CO react with photocatalyst at normal temperature and pressure 2 And H 2 O is converted into energy or high value-added chemicals, and because solar energy is inexhaustible, compared with the cyclic utilization of carbon resources of thermal catalysis and electrocatalysis, photocatalysis is more in line with the sustainable development concept and is ideal CO 2 Transformation and reuse routes.
Active site pair of catalyst in photocatalytic reaction to CO 2 The adsorption process is crucial, but the active site of the photocatalyst still cannot react with CO under normal temperature and pressure conditions 2 High density contact is made which results in a slow delay of the adsorption process throughout the catalytic process. Thus, the catalytic capability of the photocatalyst can be improved by increasing the CO content of the catalyst 2 The adsorption capacity is used for achieving the purpose. At present, a means for improving the adsorption capacity is to construct porous materials to improve the adsorption capacity of the materials, and a covalent organic framework material (COFs) serving as a crystalline porous material is a classic crystalline porous material covalent organic framework material (COFs) due to large specific surface area and crystalline structure and structural adjustability, and is a crystalline porous framework material with a stable structure developed after MOFs. The porous structure is a two-dimensional or three-dimensional porous structure constructed by orderly connecting organic molecules by strong covalent bonds (such as C ═ N, C-N and C ═ C bonds). As crystalline porous structural materials, COFs have an outstanding specific surface area and gas adsorption capacity and an outstanding specific surface area and gas adsorption capacity. COFs have the outstanding advantage of high stability under water, organic solvents and acidic and basic conditions. And metal sites with strong adsorption capacity and high catalytic activity can be simultaneously constructed by introducing metal ions. In addition, COFs of two-dimensional structure (2D) are mostly formed by connecting rigid conjugated structural monomers, and molecules have large plane conjugated systems and strong interlayer strengthSuch intra-and inter-layer conjugation facilitates charge transport and visible light absorption by the material. Currently, COFs have become a new class of visible light responsive catalysts.
Disclosure of Invention
The invention aims to provide a synthesis method of a novel compound, a preparation method of a Salen covalent organic framework-containing material and an application of the Salen covalent organic framework-containing material in photocatalytic gas-solid carbon dioxide reduction.
The technical scheme adopted by the invention is as follows:
a covalent organic framework material containing a Salen structure, characterized in that the structural unit belongs to the space group of the hexagonal system P3, and the unit cell parameter a is
b is
c is
Alpha is 90 degrees, beta is 90 degrees and gamma is 120 degrees.
The synthesis method of the novel compound is characterized by comprising the following steps: (1) 1,3, 5-triazine-2, 4, 6-tri (4 '-hydroxy-3' -methoxyl) benzene, hexamethylene tetramine and trifluoroacetic acid are added into a round-bottom flask at one time, heated and refluxed at the temperature of 80-100 ℃, reacted for 5-10 hours and hydrolyzed by glacial acetic acid.
And (2) filtering the crude product obtained in the step (1), washing the crude product with glacial acetic acid, dichloromethane and ethanol for multiple times until the filtrate is colorless, and maintaining the filtrate in a vacuum drying oven at the temperature of 100-150 ℃ for 24-120 hours to evaporate the solvent to obtain a novel yellow solid compound.
Weighing 1,3, 5-triazine-2, 4, 6-tri (4 '-hydroxy-3' -methoxy) benzene and hexamethylene tetramine in the amount ratio of 2: 3-3: 2 in the step (1) into a round-bottom flask.
The volume of the trifluoroacetic acid weighed in the step (1) is 10-50 mL.
The concentration of the glacial acetic acid substances weighed in the step (1) is 3 to up6mol L -1 The volume of the glacial acetic acid is 10-50 mL.
The preparation method of the covalent organic framework material containing the Salen structure is characterized by comprising the following steps:
(2) sequentially adding 1,3, 5-triazine-2, 4, 6-tri (4 ' -hydroxy-3 ' -methoxy-5 ' -aldehyde) benzene, ethylenediamine, dimethyl sulfoxide and ethanol into a Pyrex tube, carrying out ultrasonic treatment for 1 hour, adding an acetic acid aqueous solution, and carrying out liquid nitrogen freezing and degassing operation for three times to realize the vacuum oxygen-free condition of the reaction system; and naturally thawing the degassed Pyrex tube, putting the naturally thawed Pyrex tube into an oven, heating the Pyrex tube at 110-160 ℃ for reaction, closing the oven after 72-120 hours, and naturally cooling the Pyrex tube to room temperature.
The crude product obtained in step (2) was filtered, and washed with N, N-dimethylformamide and ethanol several times until the filtrate was colorless. And respectively carrying out solvent exchange by using methanol and acetone, and keeping the solvent in a vacuum drying oven at 100-150 ℃ for 24-72 hours to evaporate the solvent, thus obtaining a yellow powdery covalent organic framework material based on the Salen structure.
Weighing 1,3, 5-triazine-2, 4, 6-tris (4 ' -hydroxy-3 ' -methoxy-5 ' -aldehyde) benzene and ethylenediamine in a mass ratio of 2: 3-3: 2 in the step (2) into a vacuum tube.
And (3) taking dimethyl sulfoxide and ethanol with the molar ratio of 1: 2-2: 1 into a tube in the step (2).
The concentration of the substance of the acetic acid in the step (2) is 3-6mol L -1 The volume of acetic acid added is 0.3-0.5 mL.
The invention has the beneficial effects that: based on Salen structure covalent organic framework materials, due to the uniqueness of the material structure, the materials can be used as a photocatalyst to perform gas-solid photocatalytic reaction to reduce carbon dioxide into carbon monoxide.
Description of the drawings:
FIG. 1 is a synthetic scheme of an embodiment 1 of the present invention;
FIG. 2 is a nuclear magnetic spectrum of example 1 of the present invention;
FIG. 3 is a synthetic route diagram of an embodiment 2 of the present invention;
FIG. 4 an XRD diffractogram of specific example 2 of the present invention;
FIG. 5 is an infrared spectrum of an embodiment 2 of the present invention;
FIG. 6 is a graph showing the photocatalytic gas-solid carbon dioxide reduction performance in example 2 of the present invention.
The specific implementation mode is as follows:
the invention is further illustrated in detail below with reference to examples:
a covalent organic framework material containing a Salen structure, characterized in that the structural unit belongs to the space group of the hexagonal system P3, and the unit cell parameter a is
b is
c is
Alpha is 90 degrees, beta is 90 degrees and gamma is 120 degrees.
The process for preparing the above novel compound is characterized by comprising the steps of: (1) 1,3, 5-triazine-2, 4, 6-tri (4 '-hydroxy-3' -methoxyl) benzene, hexamethylene tetramine and trifluoroacetic acid are added into a round bottom flask at one time, heated and refluxed at the temperature of 80-100 ℃, reacted for 5-10 hours and hydrolyzed by glacial acetic acid.
And (2) filtering the crude product obtained in the step (1), washing the crude product with glacial acetic acid, dichloromethane and ethanol for multiple times until the filtrate is colorless, and keeping the filtrate in a vacuum drying oven at the temperature of 100-150 ℃ for 24-120 hours to evaporate the solvent to obtain a novel yellow solid compound.
Weighing 1,3, 5-triazine-2, 4, 6-tri (4 '-hydroxy-3' -methoxy) benzene and hexamethylene tetramine in the amount ratio of 2: 3-3: 2 in the step (1) into a round-bottom flask.
The volume of the trifluoroacetic acid weighed in the step (1) is 10-50 mL.
The concentration of the substance of the glacial acetic acid weighed in the step (1) is 3-6mol L -1 The volume of the glacial acetic acid is 10-50 mL.
The preparation method of the covalent organic framework material containing the Salen structure is characterized by comprising the following steps: (1) sequentially adding 1,3, 5-triazine-2, 4, 6-tri (4 ' -hydroxy-3 ' -methoxy-5 ' -aldehyde) benzene, ethylenediamine, dimethyl sulfoxide and ethanol into a Pyrex tube, performing ultrasonic treatment for 1 hour, adding an acetic acid aqueous solution, and performing liquid nitrogen freezing and degassing for three times to realize the vacuum oxygen-free condition of a reaction system; and naturally unfreezing the degassed Pyrex tube, putting the naturally unfrozen Pyrex tube into an oven, heating the Pyrex tube at 120-150 ℃ for reaction, closing the oven after 72-120 hours, and naturally cooling the Pyrex tube to room temperature.
The crude product obtained in step (2) was filtered, and washed with N, N-dimethylformamide and ethanol several times until the filtrate was colorless. And (3) respectively using methanol and acetone for solvent exchange, keeping the mixture in a vacuum drying oven at the temperature of 100-150 ℃ for 24-48 hours, and evaporating the solvent to obtain a yellow powdery covalent organic framework material based on the Salen structure.
In the step (2), benzene and ethylenediamine with the mass ratio of 2: 3-3: 2 are weighed and put into a vacuum tube.
And (3) taking dimethyl sulfoxide and ethanol with the molar ratio of 1: 2-2: 1 into a tube in the step (2).
The concentration of the substance of acetic acid in the step (2) is 3-6mol L -1 The volume of acetic acid added is 0.3-0.6 mL.
The present invention is described in more detail in the following examples, which are not intended to limit the invention thereto.
The specific embodiment is as follows:
0.49g of 1,3, 5-triazine-2, 4, 6-tris (4 '-hydroxy-3' -methoxy) benzene, 0.5g of hexamethylenetetramine, 25mL of trifluoroacetic acid were added in one portion to a round bottom flask and three liquid nitrogen freezing degassing operations were performed to test the vacuum oxygen-free condition of the reaction system. The degassed round-bottomed flask was placed in an oil bath and heated under reflux at 80 ℃ to react for 10 hours with 25mL of 6mol L -1 Glacial acetic acid is hydrolyzed. Naturally cooling, and filtering the solid. The solid product was filtered, washed with glacial acetic acid, dichloromethane, ethanol several times until the filtrate was colorless, and placed in a vacuum oven at 100 ℃ for 72 hours to evaporate the solvent, yielding 0.25g of the novel compound.
The nuclear magnetism is shown in FIG. 2, and it is clear from the figure that the peaks respectively representing the hydroxyl group, aldehyde group, benzene ring and methoxy group are seen, and the ratio of the hydroxyl group H, aldehyde group H, benzene ring H and methoxy group H is 1:1:2:3, which proves that the structure of the synthesized 1,3, 5-triazine-2, 4, 6-tri (4 ' -hydroxyl-3 ' -methoxy-5 ' -aldehyde) benzene is correct.
0.02518g of 1,3, 5-triazine-2, 4, 6-tris (4 ' -hydroxy-3 ' -methoxy-5 ' -aldehyde) benzene, 0.0055g of ethylenediamine, 1.5mL of dimethyl sulfoxide and 1.5mL of ethanol are sequentially added into a Pyrex tube, and after one hour of normal-temperature ultrasound, a pipette is used to add 0.3-0.6 mL of substances with the concentration of 3-6mol L -1 And three times of liquid nitrogen freezing and degassing operations are performed to achieve vacuum oxygen-free conditions of the reaction system. And naturally unfreezing the degassed Pyrex tube, putting the naturally unfrozen Pyrex tube into an oven, heating the Pyrex tube at 120-150 ℃ for reaction, closing the oven after 72-120 hours, and naturally cooling the Pyrex tube to room temperature. The solid product was filtered and washed with N, N-dimethylformamide and ethanol several times until the filtrate was colorless. After solvent exchange with acetone the solid powder was placed in a vacuum oven at 100 ℃ for 48 hours to evaporate the solvent, yielding 0.018g of a covalent organic framework material containing the Salen structure.
The XRD of the product and the XRD diffraction pattern of the powder of the product simulated by AA accumulation are shown in figure 4, and the peaks at 3.5 degrees, 7.3 degrees, 9.9 degrees, 11.98 degrees and 26.2 degrees respectively correspond to a 100 crystal face, a 110 crystal face, a 200 crystal face, a 120 crystal face and a 001 crystal face. As can be seen from FIG. 4, the peak patterns of the experimental spectrum and the simulated spectrum are completely consistent, which indicates that the obtained product is the covalent organic framework material containing Salen structure. The infrared spectrum is shown in FIG. 5, from which it can be seen that the obtained product is 1638cm -1 There is a strong absorption in the vicinity, corresponding to C ═ N, indicating that condensation of the two monomers has occurred.
The test chart of the reduction performance of the product of the photocatalytic gas-solid carbon dioxide is shown in figure 6, 0.010g of a uniform film made of covalent organic framework material containing a Salen structure is placed at the bottom of a reactor, a light source is started to carry out photocatalytic reaction after pure carbon dioxide is continuously introduced for a period of time, and the yield of the reduced product of carbon monoxide is up to 120 mu mol g in 5 hours -1 Average 24 per hourμmol g -1 。
Claims (10)
1. The synthesis of a novel compound, the chemical structure of which is shown in figure 1.
2. A covalent organic framework material containing a Salen structure, the chemical structure of which is shown in figure 2, and the structural unit belongs to the space group P3 of the hexagonal system, and the unit cell parameter a is
b is
c is a
Alpha is 90 degrees, beta is 90 degrees and gamma is 120 degrees.
3. A process for the preparation of the novel compound of claim 1, further comprising the steps of:
(1) 1,3, 5-triazine-2, 4, 6-tri (4 '-hydroxy-3' -methoxyl) benzene, hexamethylene tetramine and trifluoroacetic acid are added into a round-bottom flask at one time, heated and refluxed at the temperature of 80-100 ℃, reacted for 5-10 hours and hydrolyzed by glacial acetic acid. And (2) filtering the crude product obtained in the step (1), washing the crude product with glacial acetic acid, dichloromethane and ethanol for multiple times until the filtrate is colorless, and keeping the filtrate in a vacuum drying oven at the temperature of 100-150 ℃ for 24-120 hours to evaporate the solvent to obtain a novel yellow solid compound.
4. A process for the preparation of the novel compounds according to claim 1. The method is characterized in that 1,3, 5-triazine-2, 4, 6-tri (4 '-hydroxy-3' -methoxyl) benzene and hexamethylene tetramine with the weight ratio of 2: 3-3: 2 are weighed in the step (1) and put into a round-bottom flask.
5. A process for the preparation of the novel compounds according to claim 1. The method is characterized in that the volume of trifluoroacetic acid weighed in the step (1) is 10-50 mL, and the concentration of glacial acetic acid weighed in the step (1) is 3-6mol L -1 The volume of the glacial acetic acid is 10-50 mL.
6. A method for preparing a covalent organic framework material comprising a Salen structure according to claim 2, said method comprising the steps of:
(1) 1,3, 5-triazine-2, 4, 6-tri (4 ' -hydroxy-3 ' -methoxy-5 ' -aldehyde group) benzene, ethylenediamine, dimethyl sulfoxide and ethanol are added into a Pyrex tube at one time, acetic acid aqueous solution is added after 1 hour of ultrasonic treatment, and three times of liquid nitrogen freezing saliva abandoning operation are carried out to realize the vacuum anaerobic condition of the reaction system; naturally unfreezing the degassed Pyrex tube, putting the naturally unfrozen Pyrex tube into an oven, heating the Pyrex tube at 110-160 ℃ for reaction, and closing the oven after 72-120 hours to naturally cool the Pyrex tube to room temperature;
and (2) filtering the crude product obtained in the step (1), washing the crude product with N, N-dimethylformamide and ethanol for multiple times until the filtrate is colorless, performing solvent exchange with methanol and acetone respectively, and maintaining the filtrate in a vacuum drying oven at 100-150 ℃ for 24-120 hours to evaporate the solvent to obtain a yellow powdery covalent organic framework material containing a Salen structure.
7. The method of claim 2, wherein the covalent organic framework material comprises a Salen structure. The method is characterized in that 1,3, 5-triazine-2, 4, 6-tris (4 ' -hydroxy-3 ' -methoxy-5 ' -aldehyde) benzene and ethylenediamine are weighed in the amount ratio of 2: 3-3: 2 in the step (1) and put into a vacuum tube.
8. The method of claim 2, wherein the molar ratio of 1: 2-2: 1 dimethyl sulfoxide and ethanol in a tube.
9. The method for preparing a covalent organic framework material containing a Salen structure according to claim 2, wherein the concentration of the substance of acetic acid in step (1) is 3-6mol L -1 The volume of the added acetic acid is 0.3-0.6 mL.
10. The covalent organic framework material comprising Salen structure of claim 2, which can be used as a photocatalyst to perform a gas-solid photocatalytic reaction to reduce carbon dioxide to carbon monoxide due to the uniqueness of the material structure.
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| WO2014118799A1 (en) * | 2013-02-01 | 2014-08-07 | Council Of Scientific & Industrial Research | Recyclable chiral catalyst for asymmetric nitroaldol reaction and process for the preparation thereof |
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| WO2014118799A1 (en) * | 2013-02-01 | 2014-08-07 | Council Of Scientific & Industrial Research | Recyclable chiral catalyst for asymmetric nitroaldol reaction and process for the preparation thereof |
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