CN111454459A - Covalent organic framework material of bionic photosystem I, preparation and application thereof - Google Patents
Covalent organic framework material of bionic photosystem I, preparation and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 55
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- 239000001257 hydrogen Substances 0.000 claims abstract description 24
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- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
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- -1 (5-fluorobenzo [ c ] [1,2,5] thiadiazole-4, 7-diyl) bis (acetylene-2, 1-diyl) Chemical group 0.000 claims description 18
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 18
- XDTZQQXBFDIDSL-UHFFFAOYSA-N 4-[3,6,8-tris(4-aminophenyl)pyren-1-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C1=CC=C23)=CC(C=4C=CC(N)=CC=4)=C(C=C4)C1=C2C4=C(C=1C=CC(N)=CC=1)C=C3C1=CC=C(N)C=C1 XDTZQQXBFDIDSL-UHFFFAOYSA-N 0.000 claims description 16
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- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to synthesis of a functionalized covalent organic framework and an application technology thereof in the aspect of hydrogen production by photolysis of water, and creatively simulates the structure and reaction mechanism of a photosynthesis reaction center in the nature to design and develop a covalent organic framework material as a novel light-capturing material. The crystalline material is formed by covalent bonding of imino bonds formed by Schiff base condensation reaction of organic monomers. The covalent organic framework material obtained by the method has larger specific surface area, regular pore channel structure with adjustable pore diameter, and is beneficial to mass transfer of reactants and products in the catalytic process. The covalent organic framework material has high stability and durability for hydrogen production by catalyzing water decomposition under visible light, and the hydrogen production rate can reach 11.6mmol/g/h at most.
Description
Technical Field
The invention belongs to the field of organic functional materials, and particularly relates to a covalent organic framework material (COFs), a synthetic method and application thereof.
Background
Photosynthesis is one of the most efficient modes for solar energy conversion in nature, and the photosynthesis in nature is performed through the synergistic effect of a series of enzymes and other protein molecules, particularly, PSI (P700) in the photosynthesis is mature, and the apparent quantum efficiency can reach 100%. Research on the reaction principle of the photosynthetic system and simulation of the photosynthetic system to realize efficient solar energy conversion are one of the most effective means for designing and synthesizing novel light-capturing materials and improving the solar energy utilization rate at present.
As a functional porous material emerging in recent years, a covalent organic framework material has the advantages of high specific surface area, adjustable pore channel size, various structures, easiness in modification, excellent thermal stability, excellent chemical stability and the like, and is rapidly developed in the fields of gas adsorption and separation, sensors, catalysis and the like. How to design the functionalized porous frame material more effectively is a major research topic, and no precedent for constructing the porous frame material based on the bionic principle exists at present. Aiming at the defects of narrow photoresponse range, high recombination rate of photon-generated carriers and the like of the traditional single photocatalytic material, the covalent organic framework material creatively simulates the structural design of PSI (P700) and serves as a light-capturing material, and the high-efficiency material for producing hydrogen by photolysis of water is developed by utilizing the excellent characteristics of high symmetry, high stability, high specific surface area, porosity and the like. A series of covalent organic framework materials with bionic PSI structures are successfully synthesized by simulating the structure of PSI, bionically designing the positions of an electron donor and an electron acceptor in a covalent organic framework material monomer, and adjusting the electron-withdrawing capability of the electron acceptor.
At present, light-driven water decomposition hydrogen production and solar cells are the most common modes for realizing light energy conversion, and the key for realizing high-efficiency light energy utilization rate is the selection of a photocatalyst. Therefore, the design and application of high-performance photocatalysts are one of the most important parts in research. At present, most of materials used for photocatalysis are inorganic (Ti, Ga, Si, W and the like) semiconductor materials, but the inorganic semiconductor materials have the defects of poor designability, large forbidden band bandwidth, difficult adjustment and low light utilization efficiency. Therefore, a need to solve the problem in the field of photocatalysis is to continuously search for new photocatalytic materials with better absorption in the visible light region.
The COFs and the pore channels thereof can be designed, regulated and modified to have expected functions. On the other hand, different from the traditional organic polymer, the porous frame material has good crystallinity, a determined structure and a pore channel environment, and is convenient for researching and analyzing the action mechanism of the porous frame material so as to continuously improve and optimize the performance of the material. In addition, the COFs material has flexible components and structure and strong designability, so the method can be used for biomimetic design of novel porous frame materials in other fields, meets different application requirements, and has wide application value. At present, a subject group begins to pay attention to the research on the water photolysis of COFs, but the synthesis of COFs by using the structural design of bionic PSI and the application of COFs in related fields are not seen so far.
Disclosure of Invention
The invention aims to provide a method for synthesizing a covalent organic framework material, which creatively synthesizes the covalent organic framework material constructed by dialdehyde monomers with a bionic PSI structure aiming at the structure and action principle of a photosynthesis reaction center PSI (P700), and uses the covalent organic framework material as a photocatalyst for light energy conversion to realize water decomposition and hydrogen production.
In one aspect, the invention provides a covalent organic framework material, which is characterized in that the covalent organic framework material is obtained by Schiff base condensation of an organic monomer 1,3,6, 8-tetra- (p-aminophenyl) -pyrene and a dialdehyde monomer simulating a bionic photosystem I (PS I) structure.
Preferably, the electron donor of the dialdehyde monomer is symmetrically distributed on both sides of the electron acceptor.
Preferably, the dialdehyde monomer is (a)4,4' - ((5-fluorobenzo [ c ] [1,2,5] thiadiazole-4, 7-diyl) bis (acetylene-2, 1-diyl)) benzaldehyde, (b)4,4' - ((5, 6-difluorobenzo [ c ] [1,2,5] thiadiazole-4, 7-diyl) bis (acetylene-2, 1-diyl)) benzaldehyde, (c)4,4' - (benzo [ c ] [1,2,5] thiadiazole-4, 7-diyl bis (acetylene-2, 1-diyl)) benzaldehyde, (d)4,4' - (1, 4-benzenedi (acetylene-2, 1-diyl)) benzaldehyde, (e)4,4' - ((5-fluoro-6-methoxybenzo [ c ] [1,2,5] thiadiazole-4, 7-diyl) bis (acetylene-2, 1-diyl)) benzaldehyde, or (f)4,4' - (thiophene-2, 5-diyl bis (acetylene-2, 1-diyl)) benzaldehyde.
Preferably, the covalent organic framework material has a pore size of 0.5-3.5 nm.
In another aspect, the present invention provides a method for preparing a covalent organic framework material, comprising the steps of:
1) adding organic monomers 1,3,6, 8-tetra- (p-aminophenyl) -pyrene and dialdehyde monomers into a reaction vessel, and reacting by taking acetic acid as a catalyst;
2) after the reaction is finished, purifying a product;
3) purified product is subjected to supercritical CO2And carrying out intermediate treatment or heating treatment under vacuum condition to obtain the final product.
Preferably, in the reaction liquid, the molar ratio of the 1,3,6, 8-tetra- (p-aminophenyl) -pyrene to the aldehyde monomer having the biomimetic PS I structure is 1 (1-4), and the preferred ratio is 1: 2.
Preferably, the initial concentration of 1,3,6, 8-tetra- (p-aminophenyl) -pyrene in the reaction solution is 1-100 g/L, preferably 10-20 g/L.
Preferably, the concentration of the acetic acid catalyst is 1 to 18 mol/L, preferably 3 to 9 mol/L.
Preferably, the molar amount of the acetic acid catalyst is 0.2 to 40 times of the molar amount of the 1,3,6, 8-tetra- (p-aminophenyl) -pyrene.
Preferably, the pressure of the reaction system is 0 to 1 atm.
Preferably, the covalent organic framework is synthesized at a temperature of 20-200 deg.C, preferably 20-150 deg.C.
Preferably, the reaction can be carried out under heating reflux, or in a sealed reactor, or in an open container for 2-240h, preferably 72-120 h.
The technical scheme adopted by the invention for achieving the aim is that an organic monomer 1,3,6, 8-tetra- (p-aminophenyl) -pyrene and a dialdehyde monomer with a bionic PS I structure are added into a reaction vessel, the two monomers are uniformly mixed by ultrasonic treatment as shown in figure 3, acetic acid is used as a catalyst, the reaction lasts for 12-120 hours at the temperature of 20-150 ℃, and the concentration of the acetic acid catalyst is (1-18 mol/L).
On the other hand, the covalent organic framework material of the invention can be used for the light-driven hydrogen production by water decomposition.
Preferably, the light drive is a solar drive
Preferably, the covalent organic framework material obtained by the method has good photocatalytic performance, and can be used for hydrogen production through water decomposition by taking ascorbic acid as a sacrificial agent and platinum nanoparticles as a cocatalyst under illumination.
Preferably, the loading of platinum nanoparticles is 0.5-15% wt of the amount of COFs, with an optimal loading of 3-6% wt.
Preferably, the concentration of ascorbic acid is 0.1-5 mol/L, with an optimum concentration of 0.5-2 mol/L.
The photocatalytic activity test shows that the obtained covalent organic framework material has stable hydrogen generation rate and stable cyclic catalytic activity.
Preferably, the obtained covalent organic framework material has a bionic construction unit, so that the covalent organic framework material is favorable for light absorption, has a larger specific surface area and a regular and adjustable pore structure, and is favorable for efficient utilization of catalytic active sites and mass transfer of reactants and products in the reaction process.
Description of the drawings:
FIG. 1: dialdehyde monomer with bionic PS I structure.
FIG. 2: schematic diagram of covalent organic framework material constructed by bionic principle.
FIG. 3: and (3) construction of a bionic PS I covalent organic framework.
FIG. 4: PXRD of biomimetic PS I covalent organic frameworks.
FIG. 5: the bionic PS I covalent organic framework material is used for measuring the activity and stability of light-driven water decomposition and comparing the activity with the activity of other traditional photocatalysts.
The specific implementation mode is as follows:
unless otherwise indicated in the context of the present application, the technical terms and abbreviations used in the present application have the conventional meanings known to those skilled in the art; the starting compounds used in the examples described below are all commercially available unless otherwise indicated.
According to the invention, the synthesis of COFs material, the characterization test of various properties, and the specific implementation mode are as follows. Rather, the following examples are intended only to further illustrate and explain the present invention and should not be taken as limiting the scope of the invention, which is defined only by the claims.
Examples 1 to 6 are synthetic methods of biomimetic COFs, and examples 7 to 10 are experiments of obtaining the photolysis water hydrogen production experiment of biomimetic COFs
Example 1:
the synthesis of the covalent organic framework material NKCOF-108 with the bionic structure comprises the following specific implementation steps:
separately weighing the monomers 4,4' - ((5-fluorobenzo [ c ])][1,2,5]Thiadiazole-4, 7-diyl) bis (acetylene-2, 1-diyl)) benzaldehyde (0.04mmol) and 1,3,6, 8-tetrakis- (p-aminophenyl) -pyrene (0.02mmol) were added to a thick-walled heat-resistant glass tube (o.d. × i.d.: 10 × 8 mm)2) Then 0.95M L mesitylene, 0.05M L n-butanol and 0.1M L6M acetic acid aqueous solution are added, then the mixture is quickly frozen in liquid nitrogen, then the vacuum is pumped, then the tube is sealed by flame of an oxyhydrogen machine, the sealed glass tube is put into an oven at 120 ℃ for 5 days to react, and a dark red solid product NKCOF-108 is obtained, wherein PXRD is shown in figure 4.
Example 2:
the synthesis of the covalent organic framework material NKCOF-109 with the bionic structure comprises the following specific implementation steps:
the monomers 4,4' - ((5, 6-difluorobenzo [ c ]) were weighed separately][1,2,5]Thiadiazole-4, 7-diyl) bis (acetylene-2, 1-diyl)) benzaldehyde (0.04mmol) and 1,3,6, 8-tetrakis- (p-aminophenyl) -pyrene (0.02mmol) were added to a thick-walled heat-resistant glass tube (o.d. × i.d.: 10 × 8 mm)2) Then 0.1M L mesitylene, 0.9M L n-butanol and 0.1M L6M acetic acid aqueous solution are added, then the mixture is quickly frozen in liquid nitrogen, then the vacuum is pumped, then the tube is sealed by flame of an oxyhydrogen machine, the sealed glass tube is put into an oven at 120 ℃ for 5 days to react, and a dark red solid product NKCOF-109 is obtained, wherein PXRD is shown in figure 4.
Example 3:
the synthesis of the covalent organic framework material NKCOF-110 with the bionic structure comprises the following specific implementation steps:
separately weighing the monomer 4,4' - (benzo [ c ]][1,2,5]Thiadiazole-4, 7-diylbis (acetylene-2, 1-diyl)) benzaldehyde (0.04mmol) and 1,3,6, 8-tetrakis- (p-aminophenyl) -pyrene (0.02mmol) were added to a thick-walled heat-resistant glass tube (o.d. × i.d.: 10 × 8 mm)2) Then 0.75m L mesitylene and 0 are added.25M L n-butanol and 0.1M L6M aqueous acetic acid were rapidly frozen in liquid nitrogen, evacuated and then sealed with oxyhydrogen flame, and the sealed glass tube was placed in an oven at 120 ℃ for 5 days to obtain the NKCOF-110 as a dark red solid product, the PXRD of which is shown in FIG. 4.
Example 4:
the synthesis of the covalent organic framework material NKCOF-111 with bionic structure comprises the following specific steps:
the monomers 4,4' - (1, 4-benzenedi (acetylene-2, 1-diyl)) benzaldehyde (0.04mmol) and 1,3,6, 8-tetra- (p-aminophenyl) -pyrene (0.02mmol) were weighed separately and charged into a thick-walled heat-resistant glass tube (o.d. × i.d.: 10 × 8mm2) Then 0.5M L o-dichlorobenzene, 0.5M L n-butanol and 0.1M L6M acetic acid aqueous solution are added, then the mixture is quickly frozen in liquid nitrogen, vacuumized and then flame-sealed by an oxyhydrogen machine, and the sealed glass tube is put into an oven at 120 ℃ for 5 days to react to obtain a yellow solid product NKCOF-111, wherein PXRD is shown in figure 4.
Example 5:
the synthesis of the covalent organic framework material NKCOF-112 with bionic structure comprises the following specific steps:
the monomers 4,4' - ((5-fluoro-6-methoxybenzo [ c ]) were weighed separately][1,2,5]Thiadiazole-4, 7-diyl) bis (acetylene-2, 1-diyl)) benzaldehyde (0.04mmol) and 1,3,6, 8-tetrakis- (p-aminophenyl) -pyrene (0.02mmol) were added to a thick-walled heat-resistant glass tube (o.d. × i.d.: 10 × 8 mm)2) Then 0.25M L mesitylene, 0.75M L n-butanol and 0.1M L6M acetic acid aqueous solution are added, then the mixture is quickly frozen in liquid nitrogen, then the vacuum is pumped, then the tube is sealed by flame of an oxyhydrogen machine, the sealed glass tube is put into an oven at 120 ℃ for 5 days to react, and a dark red solid product NKCOF-112 is obtained, wherein PXRD is shown in figure 4.
Example 6:
the synthesis of the covalent organic framework material NKCOF-113 with the bionic structure comprises the following specific implementation steps:
monomers 4,4' - (thiophene-2, 5-diylbis (acetylene-2, 1-diyl)) benzaldehyde (0.04mmol) and 1,3,6, 8-tetrakis- (p-aminophenyl) -pyrene (0.02mmol) were weighed out separately and charged into a thick-walled heat-resistant glass tube (o.d. × i.d.: 10 × 8mm2) Then 0.75M L mesitylene, 0.25M L n-butanol and 0.1M L6M acetic acid aqueous solution are added, then the mixture is quickly frozen in liquid nitrogen, then the vacuum is pumped, then the tube is sealed by flame of an oxyhydrogen machine, the sealed glass tube is put into an oven at 120 ℃ for 5 days to react, and a dark red solid product NKCOF-113 is obtained, wherein PXRD is shown in figure 4.
Example 7:
weighing 10mg of NKCOF-108 powder into a 200M L photoreactor, adding 100M L1M ascorbic acid aqueous solution and 52 mu L50 mM chloroplatinic acid aqueous solution, placing the photoreactor containing the mixed solution into a closed system, and after complete degassing, using a 300W xenon lamp (lambda)>420nm) was directed directly into the reactor and the temperature of the photoreactor was maintained at 5 ℃. Extracting reaction gas every 1h, using argon gas as carrier gas, passing through
The molecular sieve column of (2) was subjected to gas chromatography. As shown in FIG. 5(a), NKCOF-108 shows the highest hydrogen production rate (11.6mmol/g/h), and the activity of the NKCOF-108 is not changed obviously after four cycles of tests, which indicates that the NKCOF-108 has better stability. In addition, the photolytic water hydrogen production activity of the NKCOF-108 is the highest value which can be reached by all single COFs at present. To further evaluate the activity of the present catalyst, a photocatalyst (g-C) was generally used3N4P25) and N3-COF (earlier covalent organic framework materials for photolytic hydrogen production from water, see for details reference Nature communications 2015,6,8508) water-splitting hydrogen production experiments were carried out under identical conditions. As shown in fig. 5(b), P25 has no visible light response, and therefore, no hydrogen-producing activity is exhibited under these conditions. g-C3N4，N3the-COF and the NKCOF-108 have better absorption of visible light, but the average hydrogen production rate of the NKCOF-1085 h is g-C3N4，N321 times and 172 times of-COF, which shows that NKCOF-108 has more excellent visible light catalytic hydrogen production activity.
Example 8:
10mg of NKCOF-109 powder is weighed into a 200m L photoreactor, and a photocatalytic hydrogen production experiment is carried out under the same conditions as in example 7, wherein the average hydrogen production rate of 5h is 8.6mmol/g/h, and the detailed test results are shown in the same figure 5.
Example 9:
10mg of NKCOF-110 powder is weighed into a 200m L photoreactor, and a photocatalytic hydrogen production experiment is carried out under the same conditions as in example 7, wherein the average hydrogen production rate of 5h is 3.3mmol/g/h, and the detailed test results are shown in the same figure 5.
Example 10:
10mg of NKCOF-111 powder is weighed into a 200m L photoreactor, and a photocatalytic hydrogen production experiment is carried out under the same conditions as in example 7, wherein the average hydrogen production rate of 5h is 0.8mmol/g/h, and the detailed test results are shown in the same figure 5.
Claims (10)
1. The covalent organic framework material is characterized by being obtained by condensing organic monomers 1,3,6, 8-tetra- (p-aminophenyl) -pyrene and dialdehyde monomers simulating the structure of a bionic photosystem I through Schiff base.
2. The covalent organic framework material of claim 1, characterized in that the electron donor of the dialdehyde monomer is symmetrically distributed on both sides of the electron acceptor.
3. The covalent organic framework material of claim 1 or 2, wherein the dialdehyde monomer is (a)4,4'- ((5-fluorobenzo [ c ] [1,2,5] thiadiazole-4, 7-diyl) bis (acetylene-2, 1-diyl)) benzaldehyde, (b)4,4' - ((5, 6-difluorobenzo [ c ] [1,2,5] thiadiazole-4, 7-diyl) bis (acetylene-2, 1-diyl)) benzaldehyde, (c)4,4'- (benzo [ c ] [1,2,5] thiadiazole-4, 7-diyl bis (acetylene-2, 1-diyl)) benzaldehyde, (d)4,4' - (1, 4-benzenedi (acetylene-2, 1-diyl)) benzaldehyde, (e)4,4'- ((5-fluoro-6-methoxybenzo [ c ] [1,2,5] thiadiazole-4, 7-diyl) bis (acetylene-2, 1-diyl)) benzaldehyde, and (f)4,4' - (thiophene-2, 5-diylbis (acetylene-2, 1-diyl)) benzaldehyde.
4. The covalent organic framework material of claim 1, wherein the pore size of the covalent organic framework material is between 0.5 and 3.5 nm.
5. A process for the preparation of the covalent organic framework material according to any of claims 1 to 4, characterized in that it is prepared with the following steps: :
1) adding organic monomers 1,3,6, 8-tetra- (p-aminophenyl) -pyrene and dialdehyde monomers into a reaction vessel, and reacting by taking acetic acid as a catalyst;
2) after the reaction is finished, purifying a product;
3) purified product is subjected to supercritical CO2And carrying out intermediate treatment or heating treatment under vacuum condition to obtain the final product.
6. The method of claim 5, wherein the acetic acid catalyst of the preparation step 1) is used in a molar amount of 0.2 to 40 times that of 1,3,6, 8-tetrakis- (p-aminophenyl) -pyrene.
7. The method as set forth in claim 5, wherein the pressure of the reaction system in the preparation step 1) is 0 to 1atm, and the reaction temperature is 20 to 150 ℃.
8. The method of claim 5, wherein the molar ratio of the monomer 1,3,6, 8-tetra- (p-aminophenyl) -pyrene to the other dialdehyde monomer is 1 (1-4).
9. Use of the covalent organic framework material of claim 1 for light-driven hydrogen production by water decomposition.
10. Use according to claim 9, wherein the light drive is a solar light drive.
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