CN113416299A - Organic conjugated polymer photocatalyst with side chain hanging biological base - Google Patents
Organic conjugated polymer photocatalyst with side chain hanging biological base Download PDFInfo
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- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 21
- 239000011941 photocatalyst Substances 0.000 title abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 47
- 239000001257 hydrogen Substances 0.000 claims abstract description 47
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 claims abstract description 39
- 230000001699 photocatalysis Effects 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 3
- 239000002861 polymer material Substances 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 229920000620 organic polymer Polymers 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- -1 amino, carbonyl Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 229920000642 polymer Polymers 0.000 abstract description 14
- 230000002349 favourable effect Effects 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 description 4
- 229930024421 Adenine Natural products 0.000 description 4
- 229960000643 adenine Drugs 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- HNXQXTQTPAJEJL-UHFFFAOYSA-N 2-aminopteridin-4-ol Chemical compound C1=CN=C2NC(N)=NC(=O)C2=N1 HNXQXTQTPAJEJL-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IKJFYINYNJYDTA-UHFFFAOYSA-N dibenzothiophene sulfone Chemical compound C1=CC=C2S(=O)(=O)C3=CC=CC=C3C2=C1 IKJFYINYNJYDTA-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000012925 reference material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N Pd(PPh3)4 Substances [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013317 conjugated microporous polymer Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013311 covalent triazine framework Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229940087646 methanolamine Drugs 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 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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- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- 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
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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Abstract
The invention discloses an organic conjugated polymer photocatalyst with a side chain hanging with biological bases, belonging to the technical field of materials. The side chain of the organic conjugated polymer photocatalyst is hung with a biological base, and in the process of photocatalytic hydrogen production: 1) the biological basic group effectively transmits the charges excited by the photocatalyst, so that the hydrogen production efficiency is improved; 2) the biological basic group contains abundant nitrogen atoms, can form hydrogen bonds with water molecules, is favorable for the dispersion degree of the polymer in water, improves the contact area with the water and is favorable for improving the hydrogen production efficiency; 3) the polymer photocatalyst is insoluble in most 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 hanging with the biological base is successfully used for photocatalytic hydrogen production experiments, and high hydrogen production efficiency is obtained without adding any cocatalyst.
Description
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 hanging with a biological base.
Technical Field
Along with the rapid development of society, the problems of energy shortage and environmental pollution are increasingly highlighted, become important problems which are urgently needed to be solved by human beings at present, and are also important subjects which must be overcome by the sustainable development strategy of China. Countries around the world are also taking environmentally friendly renewable energy as their strategic decision. The hydrogen energy is used as clean, efficient and pollution-free green energy, and is one of the most effective methods for solving the problems of energy crisis and environmental pollution in the future. Among the many methods and approaches for producing hydrogen, photocatalytic decomposition of water by semiconductors under solar light sources is the most ideal and promising technology for producing hydrogen.
Research on photocatalytic hydrogen production has been conducted for decades, and early research has mainly focused on photocatalyst TiO2Up [ Nature,1972,238:37-38]However, due to the short response wave, low photocatalytic activity and poor solar energy conversion efficiency, a noble metal or metal oxide co-catalyst is usually required to be loaded to improve the hydrogen production performance, which greatly increases the cost [ Nature,1980,286:474-]. Then, many researchers focused on developing various types of photocatalysts such as metal oxides or composites [ Adv Mater,2012,24:229-]The photocatalytic efficiency is greatly improved, but the catalytic activity of the catalysts can be mainly embodied in an ultraviolet region, and the ultraviolet light in sunlight is only less than 5 percent and is greatly lower than the visible light occupancy rate of 43 percent in sunlight. Therefore, the commercial application of the solar photocatalytic hydrogen production technology is to be realizedThe new material for producing hydrogen by photocatalysis of the light emitting and absorbing visible light is a necessary way.
Organic semiconductor photocatalysts have been studied relatively rarely compared to inorganic semiconductor photocatalysts. The organic semiconductor has the advantages of infinite synthesis method, convenience for functional modification, easiness in regulation and control of electrical properties and optical properties and the like, so that the organic semiconductor is unique in the field of photocatalytic hydrogen production and has great development prospect. At present, organic semiconductor materials developed for photocatalytic hydrogen production mainly comprise linear conjugated polymer photocatalysts, organic conjugated microporous polymer cocatalysts, carbon nitride polymer photocatalysts, covalent triazine framework polymer photocatalysts, covalent bonded organic framework polymer photocatalysts and water-alcohol soluble organic conjugated photocatalysts. These organic semiconductor photocatalysts exhibit excellent performance, particularly in the visible region, and exhibit good hydrogen production, which many inorganic semiconductors cannot achieve.
Despite the many advantages of organic semiconductors, 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 hinder the contact between the catalyst and the water and are not beneficial to improving the hydrogen production performance; on the other hand, researchers develop a series of organic polymers which can be dissolved in common organic solvents or even water, although the contact area with water is increased and the hydrogen production efficiency is improved, the overall efficiency is still very low, and the water-soluble materials are not beneficial to recycling of the photocatalyst, so that the development of practical application is hindered.
Disclosure of Invention
In order to overcome the technical defects, the invention provides the organic conjugated polymer semiconductor material with the side chain hanging with the biological base, and the photocatalysis hydrogen production performance of the conjugated polymer material is improved.
The side chain of the polymer material is hung with biological bases: on one hand, the charges excited by the polymer can be effectively transmitted to water molecules, and the hydrogen production efficiency is improved; on the other hand, the biological basic group contains abundant nitrogen atoms, can form hydrogen bonds with water molecules, is favorable for the dispersion degree of the polymer in water, and improves the contact area with the water, thereby improving the hydrogen production efficiency; more importantly, the organic semiconductor material has higher hydrogen production efficiency under the condition of not adding a Pt cocatalyst, greatly reduces the cost of a catalytic experiment, and has important significance.
In order to achieve the purpose, the invention is realized by the following scheme: an organic conjugated polymer having pendant biobases, having the formula:
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:
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; r1Is hydrogen, halogen, C1-C12 alkyl or alkoxy; r2-R6Independently hydrogen, C1-C30 alkyl or C1-C30 alkyl, wherein one or more carbon atoms are replaced by halogen, oxygen, alkenyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano or nitro.
Further, in the above technical solution, the side chain hanging unit a is one of the following chemical structures:
wherein R is7-R9Is NH2、N(Me)2Me, Et, CN or halogen; r10Is F or Me.
Further, in the above technical solution, the method for preparing the organic conjugated polymer material with pendant bio-base on the side chain comprises the following steps:
1. reacting A compound FN-Br, A biological base A and potassium carbonate in A DMF solution to obtain A compound FN-A;
2. performing coupling reaction on FN-A and an aromatic conjugated group P with diborate ester or double tin or double triple bonds to obtain A target compound;
3. and cleaning the target compound by using an organic solvent, and drying to obtain the organic conjugated polymer.
The chemical reaction equation is as follows:
further, in the step (1), the molar ratio of FN-Br, the biological base A and the 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 the FN-A to the 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 structure of the small molecular material by Nuclear Magnetic Resonance (NMR), element analysis and the like, tests the spectral property of the polymer material by an ultraviolet-visible spectrometer, and simultaneously tests the hydrophilicity and the photocatalytic performance of the polymer material by a contact angle.
The invention has the beneficial effects
(1) The organic semiconductor material with the side chain hanging with the biological base is used for photocatalytic hydrogen production research for the first time, and the biological base can be used as a medium for transferring charges, so that the catalytic efficiency is improved. Moreover, the materials are insoluble in common organic solvents such as methanol, petroleum ether, tetrahydrofuran, chloroform and the like, and are very beneficial to recovery;
(2) the material can form hydrogen bonds with water, so that the contact area with the water is increased, and the material is beneficial to photocatalytic hydrogen production;
(3) in the photocatalysis process of the material, any cocatalyst (such as noble metal Pt) is not required to be added, so that higher catalysis efficiency can be obtained, and the cost is greatly reduced.
Drawings
FIG. 1 is a graph showing the thermogravimetric curves of the organic polymer materials obtained in examples 2 to 3 of the present invention;
FIG. 2 is a diffuse reflection absorption spectrum of a solid powder of an organic polymer material obtained in examples 2 to 3 of the present invention;
FIG. 3 is a graph showing contact angles of organic polymer materials obtained in examples 2 to 3 of the present invention;
FIG. 4 shows the hydrogen production efficiency of the organic polymer material obtained in examples 2-3 of the present invention under irradiation of UV-visible light (greater than 300 nm);
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
The 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 following examples are expressed in degrees Celsius and the pressures are at or near atmospheric. All solvents were purchased for analytical or chromatographic grade and all reactions were performed under nitrogen inert atmosphere. All reagents were obtained commercially unless otherwise indicated.
Example 1:
compound F6A-Br was synthesized according to the following equation:
in a three-necked flask, compound F6-Br (5g,7.74mmol), adenine (4.18g,31.0mmol) and K2CO3(4.27g,31.0mmol) was charged into a flask, nitrogen was purged 3 times, and 60mL of DMF was taken and charged into a reaction flask, and reacted at 30 ℃ for 24 hours. Extraction with dichloromethane, washing with brine, drying over anhydrous sodium sulfate, and column chromatography using dichloromethane/methanol/triethylamine as eluent gave compound F6A-Br in 50% yield.1H NMR(400MHz,CDCl3)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:
synthesis of Polymer F6A-DBTO2, the reaction equation is as follows:
in a three-necked flask, compound F6A-Br (0.15g,0.2mmol), DBTO2(0.094g,0.2mmol), and K were placed2CO3(2M,0.7mL) and Pd (PPh)3)4(1.5%, 3.5mg) was charged into a flask, nitrogen was purged 3 times, and 20mL of DMF was taken and charged into a reaction flask, and reacted 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, wherein the yield is 90%. Elemental analysis: c63.40; h5.23; n15.08; and S3.09.
Example 3:
synthesis of the control material, polymer F6-DBTO2, the reaction equation is as follows:
in a three-necked flask, compound F6-Br (0.098g,0.2mmol), DBTO2(0.094g,0.2mmol), and K were placed2CO3(2M,0.7mL)、Pd(PPh3)4(1.5%, 3.5mg) was charged into a flask, nitrogen was purged 3 times, and 20mL of DMF was taken and charged into a reaction flask, and reacted at 120 ℃ for 48 hours. In-line with the aboveThen respectively washing with methanol, petroleum ether, tetrahydrofuran and chloroform, and drying at 80 ℃ for 24 hours to obtain the target polymer, wherein the yield is 78%. Elemental analysis: c79.23; h7.08; and S5.13.
Example 4
Testing the hydrogen production performance of the 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 photocatalytic system CEL-PAEM-D8 produced by Beijing Zhongzhijin Jiyuan 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 and analysis are carried out through a chromatographic instrument, and the circulation is carried out once every 40 minutes, so that the corresponding hydrogen production efficiency is obtained.
FIG. 1 is a graph showing the thermal weight loss of the organic polymer materials obtained in examples 2-3, wherein the organic polymer material of the present invention has a thermal decomposition temperature of 400 ℃ or higher, has good thermal stability, and can be applied to photocatalytic hydrogen production.
FIG. 2 is a graph showing the diffuse reflection absorption spectra of the solid powders of the organic polymer materials obtained in examples 2 to 3. The organic polymer material of the invention also has wide and strong absorption in a visible light region; has good sunlight capturing capacity.
FIG. 3 is a graph showing contact angles of organic polymer materials obtained in examples 2 to 3. Compared with a reference material (the contact angle is 71.1 degrees), the polymer material (the contact angle is 46.0 degrees) with the adenine suspended on the side chain has better hydrophilicity, and is beneficial to photocatalytic hydrogen production.
FIG. 4 shows hydrogen production performance of organic polymer materials obtained in examples 2 to 3. The invention relates to a polymer material (25.21 mmoleg) with adenine hung on a side chain-1h-1) The hydrogen production efficiency is obviously higher than that of a reference material (4.02 mmoleg)-1h-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 have respective UV-visible light (greater than 300nm, hydrogen production efficiency of 25.21 mmoleg)-1h-1) And under visible light (more than 420nm, the hydrogen production efficiency is 21.93 mmoleg-1h-1) The hydrogen production performance of the catalyst. The side chain of the invention hangs adenineThe polymer material of the pterin still has stronger hydrogen production performance under visible light, which indicates that the material has good application prospect.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and all such modifications, equivalents and improvements that come within the spirit and scope of the invention are therefore intended to be included therein.
Claims (9)
1. An organic conjugated polymer with a pendant biobase in a side chain, which is characterized by the following structural formula:
wherein, P is an aromatic conjugated unit, A is a biological base; m is 0 to 28.
2. The organic conjugated polymer material with pendant biological base in the side chain as claimed in claim 1, wherein the aromatic conjugated unit P is one of the following structures:
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; r1Is hydrogen, halogen, C1-C12 alkyl or alkoxy; r2-R6Independently hydrogen, C1-C30 alkyl or C1-C30 alkyl, wherein one or more carbon atoms are replaced by halogen, oxygen, alkenyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano or nitro.
3. The organic conjugated polymer material with pendant biological base in the side chain as claimed in claim 1, wherein the pendant unit A is one of the following structures:
wherein R is7-R9Is NH2、N(Me)2Me, Et, CN or halogen; r10Is F or Me.
4. Use of the organic polymeric material according to any one of claims 1 to 3 for photocatalytic hydrogen production.
5. Use of the organic polymer material according to claim 4 for photocatalytic hydrogen production, characterized in that: in the process of catalytic hydrogen production, any cocatalyst is not required to be added.
6. A method for preparing an organic conjugated polymer with a pendant biological base chain comprises the following chemical reaction equation:
the method is characterized by comprising the following steps:
1. reacting A compound FN-Br, A biological base A and potassium carbonate in A DMF solution to obtain A compound FN-A;
2. performing coupling reaction on FN-A and an aromatic conjugated group P with diborate ester or double tin or double triple bonds to obtain A target compound;
3. the target compound was washed with an organic solvent, followed by drying at 80 ℃ for 24 hours to obtain an organic conjugated polymer.
7. The method for producing an organic conjugated polymer having pendant biobases according to claim 6, wherein: in the step (1), the molar ratio of the FN-Br to the biological base A to the potassium carbonate is 1: 4: 4, the reaction temperature is 30 ℃, and the reaction time is 24 hours.
8. The method for producing an organic conjugated polymer having pendant biobases according to claim 6, wherein: in the step (2), the molar ratio of the FN-A to the aromatic conjugated group P is 1: 1, the reaction temperature is 120 ℃, and the reaction time is 48 hours.
9. The method for producing an organic conjugated polymer having pendant biobases according to claim 6, wherein: the organic solvent in the step (3) is selected from methanol, petroleum ether, tetrahydrofuran or chloroform.
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