CN113150250B - Organic conjugated polymer and preparation method and application thereof - Google Patents

Organic conjugated polymer and preparation method and application thereof Download PDF

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CN113150250B
CN113150250B CN202110291970.1A CN202110291970A CN113150250B CN 113150250 B CN113150250 B CN 113150250B CN 202110291970 A CN202110291970 A CN 202110291970A CN 113150250 B CN113150250 B CN 113150250B
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conjugated polymer
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金耀城
黄晓锋
陈健
王首明
江永健
陈俊浩
姜雪霏
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Guangdong University of Technology
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Abstract

The invention discloses an organic conjugated polymer, a preparation method and application thereof, wherein the organic conjugated polymer adopts benzo-bi-thiophene or benzo-bi-furan as a matrix
Figure DDA0002982921690000011
The polymer has a high plane conjugated structure, a good visible light absorption range, a large specific surface area and good dispersibility in water. Therefore, the method has excellent performance of photocatalytic hydrogen production from water.

Description

Organic conjugated polymer and preparation method and application thereof
Technical Field
The invention relates to the technical field of photocatalytic water hydrogen production, in particular to an organic conjugated microporous polymer and a preparation method and application thereof.
Background
In recent years, with the continuous consumption of non-renewable resources such as petroleum, coal, natural gas and the like and the environmental pollution problem caused by the combustion of fossil fuels, people are made to realize that the development of novel clean renewable energy sources is important. The catalyst for photocatalytic water hydrogen production is developed to gradually enter the visual field of people by combining the characteristics of inexhaustible solar energy and inexhaustible hydrogen energy and the advantages of clean and pollution-free hydrogen energy, large combustion value, storage and transportation. At present, the catalyst for photolyzing water to produce hydrogen mainly comprises inorganic semiconductor materials, organic conjugated polymers and the like. The development of inorganic semiconductor materials is limited by the characteristics of small spectral response range, low quantum efficiency and the like, and organic conjugated polymers have the characteristics of various structures, easiness in modification, high electron transmission performance and the like, and become hot spots of research in recent years. The construction of donor-acceptor (D-A) type conjugated polymers is an effective strategy for the development of efficient photocatalysts. The D-A type organic conjugated microporous polymer has the characteristics of high specific surface area, various synthesis methods, high conjugation degree, strong electron transmission capability, controllable molecular energy gap and the like, and has an important function in the field of photocatalytic water hydrogen production.
However, the hydrogen production rate of the current organic conjugated polymer as a photocatalyst is not high, so that the large-scale application of the organic conjugated polymer is limited. For example, chinese patent (CN 111804338A) discloses a triazine-D-A type nitrogen-containing organic conjugated porous polymer photocatalytic material and preparation and application thereof, mainly adopts the combination of triazine and pyrazole micromolecules, and from the data, the highest hydrogen production rate (HER) is only 1000 mu molh -1 g -1 。
Disclosure of Invention
The invention provides an organic conjugated polymer for overcoming the defect of poor hydrogen production rate of photocatalytic water.
Another object of the present invention is to provide a method for preparing the organic conjugated polymer.
It is another object of the present invention to provide a photocatalyst comprising an organic conjugated polymer and applications thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
an organic conjugated polymer, the structural formula of which is shown in formula I,
Figure BDA0002982921670000021
wherein X is O, S atom; n is 50 to 10000;
wherein
Figure BDA0002982921670000022
The unit is at least one of the following structural formulas:
Figure BDA0002982921670000023
the organic conjugated polymer is prepared by taking benzo bithiophene or benzo difuran as a donor, namely dibenzo [ b, d]Thiophene 5, 5-dioxide as acceptor, through Suzuki coupling reaction. The benzo-bithiophene and the benzo-bitofuran have good aromaticity and stable monomer structure
Figure BDA0002982921670000024
The unit modifies the alpha position of the five-membered thiophene ring or the five-membered furan ring, which is beneficial to maintaining the rigidity and the flatness of the whole structure. The energy level of the front orbit of the polymer can be adjusted, the transmission of charges in the polymer framework in the process of photocatalytic water hydrogen production is improved, and the spectral absorption performance of the polymer is improved by constructing a two-dimensional structure. In addition, the polymer is powdery, has large specific surface area and good dispersibility in water, can fully contact with water, and improves the speed of hydrogen production by photolysis of water.
Preferably, said X is an S atom.
The electronegativity of the S atom is less than that of the O atom, the aromaticity of thiophene is higher than that of furan, so that the stability of the benzo-bis-thiophene is higher than that of the benzo-bis-furan, and the hydrogen production by photolysis of water can be improved.
Preferably, the
Figure BDA0002982921670000031
The structural formula of the unit is
Figure BDA0002982921670000032
Figure BDA0002982921670000033
Compared with other A structures, the structure has high fluorescence quantum yield, good chemical stability and thermal stability and stronger electron affinity, and the D-A type conjugated polymer is constructed with the weak electron-donating unit benzodithiophene, so that the intramolecular electron transmission of the polymer in the photocatalysis process is facilitated, and the photocatalysis hydrogen production rate is further improved.
Preferably, the pore size of the organic conjugated polymer is 2 to 60nm.
The organic conjugated polymer has large surface area and regular shape when the aperture is 2-60 nm, can keep good stability of the polymer in the photocatalytic water hydrogen production process to the maximum extent, and improves the hydrogen production rate of the polymer.
The invention also provides a preparation method of the organic conjugated polymer, which comprises the following steps:
under inert atmosphere, adding benzodithiophene or benzodifuran into palladium catalyst
Figure BDA0002982921670000034
Figure BDA0002982921670000035
Heating one of the organic base, the inorganic base and the organic solvent to react to obtain the organic conjugated polymer.
Preferably, the molar ratio of the benzodithiophene or benzodifuran to the palladium catalyst is 1: (0.01-0.015).
Preferably, the molar ratio of the benzodithiophene or benzodifuran to the inorganic base is 1: (5-10).
Preferably, the reaction temperature of the heating reaction is 100-160 ℃, and the reaction time is 12-60 h.
The proportion of the inorganic base to the organic solvent is 1mmol: (4-6) mL.
A photocatalyst comprising the organic conjugated polymer.
The photocatalyst is applied to photocatalytic water decomposition for hydrogen production.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides an organic conjugated polymer, which adopts benzodithiophene or benzodifuran as a matrix and
Figure BDA0002982921670000041
the unit is subjected to Suzuki coupling reaction to obtain an organic conjugated polymer, which has high light absorption capacity in the visible light range and water contentHigh dispersivity, good thermodynamic stability, up to 2500.3 mu mol in 0.2mol/L of ascorbic acid sacrificial agent -1 g -1 h -1 The photocatalytic hydrogen production rate.
Drawings
FIG. 1 is an infrared spectrum of photocatalysts P1 and P2 of examples 1 and 2;
FIG. 2 is a graph showing ultraviolet-visible absorption (Uv-vis) spectra of photocatalysts P1 and P2 of examples 1 to 2;
FIG. 3 is a graph showing the photocatalytic water splitting hydrogen production efficiency of the photocatalysts P1 and P2 in examples 1 and 2.
Detailed Description
The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
Synthesis of Polymer P1
The synthetic route is as follows:
Figure BDA0002982921670000042
accurately weighing monomer M1 (1.000mmol, 0.3741g) and monomer M2 (0.500mmol, 0.4131g), adding into a 48mL thick-walled pressure-resistant bottle, adding Pd (pph) under inert gas atmosphere 3 ) 4 (0.025mmol，29mg)，K 2 CO 3 (2 mol/L,2.5 mL) and DMF (15 mL), sealed. The reaction was carried out at 150 ℃ for 48h under protection from light. After the reaction solution is cooled to room temperature, the reaction solution is dripped into a continuously stirred methanol solution, and a crude product is obtained by filtration. The crude product is subjected to Soxhlet extraction for 24 hours respectively by using 100mL of methanol and petroleum ether in sequence, the solid of the residue is washed by using methanol and dried in vacuum for 24 hours, and a brown powdery product P1 is obtained, wherein the polymerization degree of the P1 is 4.
The photocatalyst of this example consisted of copolymer P1.
Example 2
Synthesis of Polymer P2
A representative synthetic route is as follows:
Figure BDA0002982921670000051
accurately weighing monomer M1 (1.000mmol, 0.3741g) and monomer M3 (0.500mmol, 0.4292g), adding into a 48mL thick-wall pressure-resistant bottle, adding Pd (pph) under inert gas atmosphere 3 ) 4 (0.025mmol，29mg)，K 2 CO 3 (2 mol/L,2.5 mL) and DMF (15 mL) were sealed. The reaction was carried out at 150 ℃ for 48h under exclusion of light. After the reaction solution is cooled to room temperature, the reaction solution is dripped into a continuously stirred methanol solution, and a crude product is obtained by filtration. The crude product is subjected to Soxhlet extraction for 24 hours by using 100mL of methanol and petroleum ether in sequence, and the solid of the residue is washed by the methanol and dried in vacuum for 24 hours to obtain a yellow powdery product P2, wherein the polymerization degree of the P2 is 4.
The photocatalyst of this example consisted of copolymer P2.
Example 3
The preparation process is as in example 2, except that the monomer of M1 is replaced by the monomer of A2
Figure BDA0002982921670000052
Obtaining the P3 conjugated polymer, wherein the polymerization degree of the P3 is 50.
The photocatalyst of this example consisted of copolymer P3.
Example 4
The preparation is as in example 2, with the difference that the monomer of M1 is replaced by the monomer A3
Figure BDA0002982921670000053
P4 conjugated polymer is obtained, and the polymerization degree of P4 is 50.
The photocatalyst of this example consisted of copolymer P4.
Example 5
The preparation process is as in example 2, with the difference that the monomer of M1 is replacedTo A4 monomer
Figure BDA0002982921670000061
P5 conjugated polymer is obtained, and the polymerization degree of P5 is 50.
The photocatalyst of this example consisted of copolymer P5.
Example 6
The preparation process is as in example 2, except that the monomer of M1 is replaced by the monomer A5
Figure BDA0002982921670000062
Obtaining the P6 conjugated polymer, wherein the polymerization degree of P6 is 50.
The photocatalyst of this example consisted of copolymer P6.
Example 7
The preparation is as in example 2, with the difference that the monomer of M1 is replaced by the A6 monomer
Figure BDA0002982921670000063
P7 conjugated polymer is obtained, and the polymerization degree of P7 is 50.
The photocatalyst of this example consisted of copolymer P7.
Example 8
The preparation is as in example 2, with the difference that the monomer of M1 is replaced by the monomer A3
Figure BDA0002982921670000064
Obtaining the P8 conjugated polymer, wherein the polymerization degree of P8 is 100.
The photocatalyst of this example consisted of copolymer P8.
Example 9
The preparation process is as in example 2, except that the monomer of M1 is replaced by the monomer A3
Figure BDA0002982921670000065
P9 conjugated polymer is obtained, and the polymerization degree of P9 is 1000.
The photocatalyst of the present example consisted of copolymer P9.
Example 10
The preparation is as in example 2, with the difference that the monomer of M1 is replaced by the monomer A3
Figure BDA0002982921670000071
Obtaining the P10 conjugated polymer, wherein the polymerization degree of the P10 is 10000.
The photocatalyst of this example consisted of copolymer P10.
Comparative example 1
The preparation is as in example 2, with the difference that the M3 monomer is replaced by
Figure BDA0002982921670000072
Obtaining the P8 conjugated polymer, wherein the polymerization degree of P8 is 2.
The photocatalyst of this comparative example consisted of copolymer P8.
Comparative example 2
The preparation process is as in example 2, except that the M1 monomer is replaced by
Figure BDA0002982921670000073
Obtaining the P9 conjugated polymer, wherein the polymerization degree of P9 is 2.
The photocatalyst of this comparative example consisted of copolymer P9.
The above examples and comparative examples were each subjected to a performance test
Testing the hydrogen production rate:
weighing 5mg of polymer, adding 50mL of ascorbic acid solution (0.2 mol/L), ultrasonically oscillating for 15 minutes until the polymer is completely dispersed, testing by using a Pophyiiela Labsolar 6A full-glass automatic online trace gas analysis system, and obtaining a hydrogen production rate result under full-spectrum irradiation for 6 hours.
TABLE 1 data for examples and comparative examples
Figure BDA0002982921670000074
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (7)

1. An organic conjugated polymer is characterized in that the structural formula of the organic conjugated polymer is shown as a formula I,
Figure FDA0003988592210000011
wherein X is O, S atom; n is 4;
wherein
Figure FDA0003988592210000012
Has a unit structural formula of
Figure FDA0003988592210000013
The pore diameter of the organic conjugated polymer is 2-60 nm.
2. The organic conjugated polymer according to claim 1, wherein X is an S atom.
3. The method for producing an organic conjugated polymer according to any one of claims 1 to 2, comprising the steps of:
under inert atmosphere, adding benzo bithiophene or benzo bithiofuran into palladium catalyst
Figure FDA0003988592210000014
Heating inorganic base and organic solvent to react to obtain the organic conjugated polymer.
4. The method for preparing an organic conjugated polymer according to claim 3, wherein the molar ratio of the benzodithiophene or the benzodifuran to the inorganic base is 1 (5-10).
5. The method for preparing an organic conjugated polymer according to claim 3, wherein the reaction temperature of the heating reaction is 100 to 160 ℃ and the reaction time is 12 to 60 hours.
6. A photocatalyst comprising the organic conjugated polymer according to any one of claims 1 to 2.
7. The use of the photocatalyst of claim 6 in photocatalytic decomposition of water to produce hydrogen.
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