CN113416299B - Organic conjugated polymer photocatalyst with side chain suspended biological base - Google Patents

Organic conjugated polymer photocatalyst with side chain suspended biological base Download PDF

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CN113416299B
CN113416299B CN202110755019.7A CN202110755019A CN113416299B CN 113416299 B CN113416299 B CN 113416299B CN 202110755019 A CN202110755019 A CN 202110755019A CN 113416299 B CN113416299 B CN 113416299B
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李仁龙
梁磊
路剑峰
韩会娟
牛红英
王华杰
王吉超
张万庆
李琛
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Henan Institute of Science and Technology
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Abstract

The invention discloses an organic conjugated polymer photocatalyst with a side chain suspending biological base, and belongs to the technical field of materials. The side chain of the organic conjugated polymer photocatalyst is suspended with biological base, and in the photocatalytic hydrogen production process: 1) The biological base effectively transmits charges excited by the photocatalyst, thereby being beneficial to improving the hydrogen production efficiency; 2) The biological base contains rich nitrogen atoms, can form hydrogen bonds with water molecules, is favorable for the dispersity of polymers in water, and improves the contact area with water, thereby being favorable for improving the hydrogen production efficiency; 3) The polymer photocatalyst is insoluble in a plurality of organic solvents, so that the polymer photocatalyst is favorable for recycling and is very suitable for being used as a hydrogen production photocatalyst material. The organic conjugated polymer with the side chain suspended with the biological base is successfully used for photocatalysis hydrogen production experiments, and higher hydrogen production efficiency is obtained without adding any cocatalyst.

Description

Organic conjugated polymer photocatalyst with side chain suspended biological base
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to an organic conjugated polymer photocatalyst with a side chain suspending biological base.
Technical Field
With the rapid development of society, the problems of energy shortage and environmental pollution are increasingly prominent, become the major problems to be solved by the current urgent need of human beings, and are also the major problems that the sustainable development strategy of China must be overcome. Environmentally friendly renewable energy sources are also being considered as respective strategic decisions in countries around the world. The hydrogen energy is used as a clean, efficient and pollution-free green energy source, and is one of the most effective methods for solving the energy crisis and the environmental pollution problem in the future. Among the numerous methods and pathways for producing hydrogen, the use of semiconductors to photocatalytically decompose water under solar light sources for hydrogen production is the most desirable and promising technology.
Research on photocatalytic hydrogen production has been carried out for decades, and early research has been mainly focused on photocatalytic TiO 2 Up [ Nature,1972,238:37-38 ]]However, due to the factors of short response wave, low photocatalytic activity, poor solar energy conversion efficiency and the like, a cocatalyst such as noble metal or metal oxide is usually required to be loaded to improve the hydrogen production performance, which greatly increases the cost [ Nature,1980,286:474-476 ]]. Many researchers have subsequently focused on the development of various types of photocatalysts such as metal oxides or composites [ Adv Mater 2012,24:229-251]The photocatalysis efficiency is greatly improved, but the catalytic activity of the catalyst can be mainly embodied in the ultraviolet light region, and the ultraviolet light is only less than 5% in sunlight and is greatly lower than the visible light occupancy rate of 43% in the sunlight. Therefore, to realize the commercial application of the technology of producing hydrogen by utilizing sunlight photocatalysis, the development of new materials for producing hydrogen by absorbing visible light photocatalysis is a necessary way.
Organic semiconductor photocatalysts have been relatively rarely studied relative to inorganic semiconductor photocatalysts. The organic semiconductor has the advantages of endless synthesis method, convenience in functional modification, easiness in regulation and control of electrical properties and optical properties and the like, so that the organic semiconductor stands out in the field of photocatalytic hydrogen production, and has great development prospect. At present, the developed organic semiconductor materials for photocatalytic hydrogen production mainly comprise linear conjugated polymer photocatalysts, organic conjugated microporous polymer cocatalysts, carbon nitride polymer photocatalysts, covalent triazine frame polymer photocatalysts, covalent bonding organic frame polymer photocatalysts and water-alcohol soluble organic conjugated photocatalysts. These organic semiconductor photocatalysts exhibit excellent performance, particularly in the visible region, exhibiting good hydrogen production effects, which are not achievable with many inorganic semiconductors.
While organic semiconductors have many advantages, the current hydrogen production efficiency is still relatively low, and many organic semiconductors require the addition of Pt promoters to maintain high catalytic performance. In addition, on one hand, in order to facilitate material treatment and recovery, researchers develop a series of organic polymers which are insoluble in common organic solvents and water, but the organic polymers prevent the contact of the catalyst with water, and are not beneficial to improving the hydrogen production performance; on the other hand, researchers develop a series of organic polymers which are soluble in common organic solvents and even water, although the contact area with water is increased, the hydrogen production efficiency is improved, the overall efficiency is still very low, and the water-soluble materials are very unfavorable for recycling of photocatalysts, thus preventing the development of practical application.
Disclosure of Invention
In order to overcome the technical defects, the invention provides the organic conjugated polymer semiconductor material with the side chain suspended with the biological base, which improves the photocatalytic hydrogen production performance of the conjugated polymer material.
The side chains of the polymer materials are suspended with biological bases: on one hand, the charge excited by the polymer can be effectively transmitted to water molecules, so that the hydrogen production efficiency is improved; on the other hand, the biological base contains rich nitrogen atoms, can form hydrogen bonds with water molecules, is favorable for the dispersity of polymers in water, and improves the contact area with water, thereby improving the hydrogen production efficiency; more importantly, the organic semiconductor material has higher hydrogen production efficiency under the condition of not adding Pt catalyst promoter, greatly reduces the cost of the catalytic experiment, and has important significance.
In order to achieve the above object, the present invention is realized by the following means: an organic conjugated polymer with a side chain suspending biological base, which has the following structural formula:
Figure BDA0003144650250000031
wherein P is an aromatic conjugated unit, A is a biological base; m is 0 to 28.
Further, in the above technical solution, the aromatic conjugated unit P is one of the following chemical structures:
Figure BDA0003144650250000032
Figure BDA0003144650250000041
wherein: x is N, O, S, se or Te; y is C or N; z is C, si, N; m is Zn, cu, fe, co, ni, pd or Pt; r is R 1 Is hydrogen, halogen, C1-C12 alkyl or alkoxy; r is R 2 -R 6 Independently is hydrogen, C1-C30 alkyl or a group formed by substitution of one or more carbon atoms in C1-C30 alkyl with halogen, oxygen, alkenyl, alkynyl, aryl, hydroxy, amino, carbonyl, carboxyl, ester, cyano or nitro.
Further, in the above technical solution, the side chain suspension unit a is one of the following chemical structures:
Figure BDA0003144650250000042
wherein R is 7 -R 9 Is NH 2 、N(Me) 2 Me, et, CN, or halogen; r is R 10 F or Me.
Further, in the above technical scheme, the preparation method of the organic conjugated polymer material with the side chain suspending the biological base comprises the following steps:
1. reacting compound FN-Br, biological base A and potassium carbonate in DMF solution to obtain compound FN-A;
2. FN-A and aromatic conjugated group P with double boric acid ester or double tin or double triple bond are subjected to coupling reaction to obtain A target compound;
3. and (3) cleaning the target compound by adopting an organic solvent, and drying to obtain the organic conjugated polymer.
The chemical reaction equation is as follows:
Figure BDA0003144650250000051
further, in the step (1), the molar ratio of FN-Br, biological base A and potassium carbonate is 1:4:4, the reaction temperature is 30 ℃ and the reaction time is 24 hours.
Further, in the step (2), the molar ratio of FN-A to aromatic conjugated group P is 1:1, the reaction temperature is 120 ℃, and the reaction time is 48 hours.
Further, the organic solvent in the step (3) is selected from methanol, petroleum ether, tetrahydrofuran, chloroform, etc.
The invention characterizes the structures of small molecular materials through Nuclear Magnetic Resonance (NMR), elemental analysis and the like, and the spectral properties of polymer materials are tested through an ultraviolet-visible spectrometer, the contact angle characterizes the hydrophilia of the polymer materials, and the photocatalytic performance of the polymer materials is tested.
The invention has the beneficial effects that
(1) The organic semiconductor material with the side chain suspended with the biological base is firstly used for photocatalysis hydrogen production research, and the biological base can be used as a medium for transmitting charges, thereby being beneficial to improving the catalytic efficiency. Moreover, the materials are insoluble in common organic solvents such as methanol, petroleum ether, tetrahydrofuran, chloroform and the like, and are very favorable for recovery;
(2) The material can form hydrogen bonds with water, so that the contact area with water is increased, and the material is beneficial to photocatalytic hydrogen production;
(3) In the photocatalysis process, the material can obtain higher catalysis efficiency without adding any promoter (such as noble metal Pt), thereby greatly reducing the cost.
Drawings
FIG. 1 is a graph showing the thermal weight loss of the organic polymeric materials obtained in examples 2-3 of the present invention;
FIG. 2 is a diffuse reflection absorption spectrum of the solid organic polymer material powder obtained in examples 2-3 of the present invention;
FIG. 3 shows the contact angle of the organic polymer material obtained in examples 2-3 of the present invention;
FIG. 4 shows the hydrogen production efficiency of the organic polymer materials obtained in examples 2-3 of the present invention under UV-visible (greater than 300 nm) irradiation;
FIG. 5 shows the hydrogen production efficiency of the organic polymer material obtained in example 2 of the present invention under irradiation of visible light (greater than 420 nm).
Detailed Description
Practice of the present invention may employ conventional techniques of polymer chemistry within the skill of the art. In the following examples, efforts are made to ensure accuracy with respect to numbers used (including amounts, temperature, reaction time, etc.), but some experimental errors and deviations should be accounted for. The temperatures used in the examples below are in degrees Celsius and the pressure is at or near atmospheric. All solvents were purchased for analytical grade or chromatographic grade and all reactions were carried out under nitrogen inert atmosphere. All reagents were commercially available unless otherwise indicated.
Example 1:
the compound F6A-Br was synthesized according to the following reaction equation:
Figure BDA0003144650250000071
in a three-port flask, compound F6-Br (5 g,7.74 mmol), adenine (4.18 g,31.0 mmol) and K 2 CO 3 (4.27 g,31.0 mmol) was added to the flask, nitrogen was purged 3 times, 60mL of DMF was taken and added to the reaction flask, and the reaction was carried out at 30℃for 24 hours. Extracting with dichloromethane, washing with saline, drying with anhydrous sodium sulfate, and separating by column chromatography with dichloromethane/methanol/triethylamine as eluent to obtain compound F6A-Br with 50% yield. 1 H NMR(400MHz,CDCl 3 )δ8.34(s,2H),7.71(s,2H),7.51(d,J＝8.0,2H),7.45(d,J＝8.0,2H),7.39(s,2H),5.52(s,4H),4.10-4.06(t,J＝8.0Hz,4H),1.89-1.85(m,4H),1.74-1.68(m,4H),1.10(s,8H),0.56-0.52(m,4H).
Example 2:
the polymer F6A-DBTO2 was synthesized according to the following reaction equation:
Figure BDA0003144650250000072
in a three-necked flask, compound F6A-Br (0.15 g,0.2 mmol), DBTO2 (0.094 g,0.2 mmol), K 2 CO 3 (2M, 0.7 mL) and Pd (PPh) 3 ) 4 (1.5%, 3.5 mg) was added to the flask, nitrogen was purged 3 times, 20mL of DMF was taken and added to the reaction flask, and the reaction was carried out at 120℃for 48 hours. Then respectively washing with methanol, petroleum ether, tetrahydrofuran and chloroform, and drying at 80 ℃ for 24 hours to obtain the target polymer with the yield of 90 percent. Elemental analysis: c63.40; h5.23; n15.08; s3.09.
Example 3:
the synthesis of the control material, polymer F6-DBTO2, was performed as follows:
Figure BDA0003144650250000081
in a three-necked flask, compound F6-Br (0.098 g,0.2 mmol), DBTO2 (0.094 g,0.2 mmol), K 2 CO 3 (2M,0.7mL)、Pd(PPh 3 ) 4 (1.5%, 3.5 mg) was added to the flask, nitrogen was purged 3 times, 20mL of DMF was taken and added to the reaction flask, and the reaction was carried out at 120℃for 48 hours. Then respectively washing with methanol, petroleum ether, tetrahydrofuran and chloroform, and drying at 80 ℃ for 24 hours to obtain the target polymer with the yield of 78%. Elemental analysis: c79.23; h7.08; s5.13.
Example 4
Testing of hydrogen production performance of organic conjugated polymer photocatalyst:
5mg of polymer catalyst, 10mL of triethylamine, 10mL of methanol and 30mL of water are added into a reactor for ultrasonic treatment for 1 hour, a photocatalysis system CEL-PAEM-D8 produced by Beijing Zhongzhujin source company is adopted for testing, a xenon lamp is used as a light source, the ultraviolet-visible light range is more than 300nm, the visible light range is more than 420nm, detection analysis is carried out through a chromatographic instrument, and the corresponding hydrogen production efficiency is obtained after circulation every 40 minutes.
FIG. 1 is a graph showing the thermal weight loss of the organic polymer material obtained in examples 2-3, wherein the thermal decomposition temperature of the organic polymer material is above 400 ℃, and the organic polymer material has good thermal stability and can be applied to photocatalytic hydrogen production.
FIG. 2 is a diffuse reflectance absorption spectrum of the solid organic polymer material powder obtained in examples 2 to 3. The organic polymer material has wide and strong absorption in the visible light region; has good sunlight capturing capability.
FIG. 3 shows the contact angle of the organic polymer material obtained in examples 2-3. The polymer material (contact angle is 46.0 DEG) of the side chain suspended adenine has better hydrophilicity than the reference material (contact angle is 71.1 DEG), and is beneficial to photocatalytic hydrogen production.
FIG. 4 shows the hydrogen generating properties of the organic polymer materials obtained in examples 2 to 3. The polymer material of the present invention (25.21 mmolg -1 h -1 ) The hydrogen production efficiency is obviously higher than that of a reference material (4.02 mmolge -1 h -1 ) The superiority of the side chain suspended adenine polymer material is proved.
FIG. 5 shows that the organic polymer materials obtained in example 2 show a hydrogen production efficiency of 25.21 mmolgs under UV-visible light (greater than 300 nm) -1 h -1 ) And under visible light (greater than 420nm, hydrogen production efficiency of 21.93 mmolgs) -1 h -1 ) Hydrogen production performance of (a). The polymer material with the adenine suspended in the side chain still has strong hydrogen production performance under visible light, which shows that the material has good application prospect.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and all changes, equivalents, and modifications that come within the spirit and scope of the invention are desired to be construed as being within the scope of the invention.

Claims (2)

1. Application of organic polymer material in photocatalytic hydrogen production, wherein the organic polymer material has the structure of
Figure FDA0004175814560000011
2. Use of an organic polymeric material according to claim 1 for photocatalytic hydrogen production, characterized in that: in the catalytic hydrogen production process, no cocatalyst is needed to be added.
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