CN112159517B - Dager base conjugated microporous polymer photocatalyst and preparation method and application thereof - Google Patents
Dager base conjugated microporous polymer photocatalyst and preparation method and application thereof Download PDFInfo
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- CN112159517B CN112159517B CN202010883151.1A CN202010883151A CN112159517B CN 112159517 B CN112159517 B CN 112159517B CN 202010883151 A CN202010883151 A CN 202010883151A CN 112159517 B CN112159517 B CN 112159517B
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- microporous polymer
- conjugated microporous
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- troger
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- 239000013317 conjugated microporous polymer Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000011941 photocatalyst Substances 0.000 title description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000001699 photocatalysis Effects 0.000 claims abstract description 14
- 230000009467 reduction Effects 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 13
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 7
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000005691 oxidative coupling reaction Methods 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 230000031700 light absorption Effects 0.000 abstract description 2
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 48
- 239000002585 base Substances 0.000 description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 239000002244 precipitate Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000003513 alkali Substances 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000000944 Soxhlet extraction Methods 0.000 description 6
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- SXPSZIHEWFTLEQ-UHFFFAOYSA-N tröger's base Chemical compound C12=CC=C(C)C=C2CN2C3=CC=C(C)C=C3CN1C2 SXPSZIHEWFTLEQ-UHFFFAOYSA-N 0.000 description 3
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000000985 reflectance spectrum Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- ZDRMMTYSQSIGRY-UHFFFAOYSA-N 1,3,5-triethynylbenzene Chemical compound C#CC1=CC(C#C)=CC(C#C)=C1 ZDRMMTYSQSIGRY-UHFFFAOYSA-N 0.000 description 1
- MVLGANVFCMOJHR-UHFFFAOYSA-N 1,4-diethynylbenzene Chemical compound C#CC1=CC=C(C#C)C=C1 MVLGANVFCMOJHR-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- 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
- C08G61/124—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 nitrogen atom in the ring
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Abstract
The invention discloses a troger base conjugated microporous polymer and a preparation method thereof, and the material is prepared by taking diiodo troger base and carbazole or aromatic diyne and trialkyne compounds as raw materials through oxidation coupling or Sonogashira coupling copolymerization reaction. The conjugated microporous polymer has a V-shaped rigid skeleton structure, high physical and chemical stability, strong gas adsorption capacity, large specific surface area and strong visible light absorption capacity, and can be applied to photocatalytic pollutant degradation, water decomposition and CO 2 The field of reduction.
Description
Technical Field
The invention belongs to the technical field of photoelectric functional materials, and particularly relates to a troger base conjugated microporous polymer, a preparation method and a photocatalytic application thereof.
Background
The organic frameworks of the conjugated microporous polymers are completely connected in a pi-electron conjugated mode through benzene rings and carbon-carbon triple bonds, and a foundation is provided for the application of the conjugated microporous polymers in the fields of photoelectricity, energy storage, sensing and the like. Since coper 2007 reported that the first polyarylene-based conjugated microporous polymer to date, numerous conjugated microporous polymers with different structures and properties were continuously developed. Although the material does not have a long procedural program, the reaction condition for synthesizing the material is mild, so that the material is very suitable for constructing a functionalized novel conjugated microporous polymer by using a functionalized monomer, and the adjustment of the pore structure and the specific surface area can be effectively realized by changing the length of the link between conjugated structures or the configuration of the conjugated monomer. Patent CN110394187A discloses a preparation method and application of a nitrogen and iron doped conjugated microporous carbon material, and the material is simple to prepare, convenient to control and good in oxygen reduction catalytic activity. However, the material is mainly used as a fuel cell anode, and the metal element is used as a catalytic active site. Patent CN109942570A discloses a phenothiazine-based conjugated microporous polymer, and the material is used for photocatalytic oxyselenization of indole, but the conjugated microporous polymer mainly embodies ultraviolet absorption, and is insufficient in absorption and utilization of visible light.
Disclosure of Invention
The invention aims to provide a troger base conjugated microporous polymer and a preparation method thereof, the polymer has the advantages of simple preparation process, controllable structure, higher specific surface area and good visible light responsiveness, and can be applied to photocatalytic pollutant degradation, water decomposition and CO 2 Reduction and conversion, etc.
The technical solution for realizing the purpose of the invention is as follows: a troger base conjugated microporous polymer having the structure of formula I or II:
wherein the content of the first and second substances,
is of the following structure
Preferably, the polymer is a powder, and the pore size distribution range of the polymer is mainly 0.5-2 nm.
Preferably, the troger base has the structure of formula IThe preparation method of the conjugated microporous polymer comprises the following steps: preparing 0.1-0.2 mol/L N, N-dimethylformamide solution of diiodo troger base, adding carbazole into the diiodo troger base solution with the molar ratio of the diiodo troger base to the carbazole being 1:4, dispersing potassium carbonate, cuprous iodide and 1, 10-phenanthroline into the solution with the molar ratio of the diiodo troger base to potassium carbonate, cuprous iodide and 1, 10-phenanthroline being 100:400:10:1, reacting at 150 ℃ for 24 hours under the protection of nitrogen, cooling to room temperature, removing the solvent, and purifying the product through column chromatography (ethyl acetate/petroleum ether is 1:3) to obtain the carbazolyl conjugated microporous polymer monomer. Preparing a chloroform solution of 0.009-0.01 mol/L carbazolyl conjugated microporous polymer monomer, and mixing the carbazolyl conjugated microporous polymer monomer with FeCl 3 In a molar ratio of 1:10, adding FeCl 3 Adding the solution into a chloroform solution of the carbazolyl conjugated microporous polymer monomer, reacting at 60 ℃ for 24 hours under the protection of nitrogen, then adding 50mL of methanol into the reaction mixture, stirring the obtained mixture for 1 hour, filtering and collecting precipitate, and washing the precipitate by using methanol, dichloromethane and acetone in sequence. The precipitate was treated with hydrochloric acid for 2 hours, filtered, and washed with water, methanol, dichloromethane, and acetone in that order. And (3) performing Soxhlet extraction by using a mixed solution of methanol and tetrahydrofuran, purifying for 24 hours, and drying to obtain the conjugated microporous polymer.
Preferably, the preparation method of the troger base conjugated microporous polymer with the structure of formula I: taking a mixed solvent of N, N-dimethylformamide and triethylamine in a volume ratio of 1:1 as a medium, preparing 0.1-0.15 mol/L diiodo troger's alkali solution, taking the molar ratio of diiodo troger's alkali to 1,3, 5-triethynyl benzene as 1.5:1, adding a tri-alkynyl monomer, and taking diiodo troger's alkali and Pd (pph) 3 ) 4 And CuI in a molar ratio of 30:1:1, adding Pd (pph) 3 ) 4 Dispersing CuI into the solution, reacting at 80 ℃ for 24 hours under the protection of nitrogen, carrying out Sonogashira coupling reaction, collecting the precipitate after the reaction, stirring the precipitate in hydrochloric acid for 1 hour, washing with water, stirring in a mixed solution of acetone, toluene and methanol for 1 hour, drying, and carrying out Soxhlet extraction by using a mixed solution of methanol and tetrahydrofuran to obtain the conjugated microporous polymer.
Preferably, the preparation method of the troger base conjugated microporous polymer with the structure of formula II comprises the following steps: taking a mixed solvent of N, N-dimethylformamide and triethylamine in a volume ratio of 1:1 as a medium, preparing 0.1-0.15 mol/L diiodo troger's alkali solution, taking the molar ratio of the diiodo troger's alkali to 1, 4-diacetylene benzene as 1.5:1, adding a dialkynyl monomer, and taking diiodo troger's alkali and Pd (pph) 3 ) 4 And CuI in a molar ratio of 30:1:1, adding Pd (pph) 3 ) 4 Dispersing CuI and CuI into the solution, reacting for 24h at 80 ℃ under the protection of nitrogen, carrying out Sonogashira coupling reaction, collecting the precipitate after the reaction, stirring the precipitate in hydrochloric acid for 1h, washing with water, stirring in a mixed solution of acetone, toluene and methanol for 1h, drying, and carrying out Soxhlet extraction by using a mixed solution of methanol and tetrahydrofuran to obtain the conjugated microporous polymer.
The invention also provides application of the troger base conjugated microporous polymer, and the conjugated microporous polymer is applied to photocatalysis CO 2 In the reduction reaction.
Compared with the prior art, the invention has the beneficial effects that:
(1) the conjugated microporous polymer is based on troger base with a V-shaped framework structure, and has a large specific surface area and good physical and chemical stability.
(2) The conjugated microporous polymer based on the troger's base has excellent CO 2 Adsorption capacity in the photocatalysis of CO 2 In the reduction conversion, the catalyst has higher reactant adsorption and activation capability.
(3) The conjugate microporous polymer based on the troger base has narrower band gap and strong visible light absorption capacity, thereby having larger application potential.
The present invention is described in further detail below with reference to the attached drawing figures.
Drawings
FIG. 1 is an infrared spectrum of the conjugated microporous polymer prepared in example 1.
FIG. 2 is a schematic representation of the conjugated microporous polymer prepared in example 1 13 C solid nuclear magnetic spectrum.
FIG. 3 shows an embodiment1 photocatalytic CO of the conjugated microporous Polymer prepared 2 Reduction performance.
FIG. 4 is a scanning electron micrograph of the conjugated microporous polymer prepared in example 1.
FIG. 5 is an infrared spectrum of the conjugated microporous polymer prepared in example 2.
FIG. 6 is a schematic representation of a conjugated microporous polymer prepared in example 2 13 C solid nuclear magnetic spectrum.
FIG. 7 shows photocatalytic CO of the conjugated microporous polymer prepared in example 2 2 Reduction performance.
FIG. 8 is an infrared spectrum of the conjugated microporous polymer prepared in example 3.
FIG. 9 is a schematic representation of a conjugated microporous polymer prepared in example 3 13 C solid nuclear magnetic spectrum.
FIG. 10 is a photo-catalytic CO of the conjugated microporous polymer prepared in example 3 2 Reduction performance.
FIG. 11 is a UV-visible diffuse reflectance spectrum of the conjugated microporous polymer prepared in example 3.
Detailed Description
The following examples are presented to enable one of ordinary skill in the art to more fully understand the present invention.
The troger base is a compound with a hundred-year research history, derivatives of the troger base all have similar V-shaped molecular frameworks, the molecular center is a methylene diazocine bridge, and aromatic hydrocarbons are respectively connected to two sides of the center of the diazocine bridge. Previously, the attention of troger's base has been focused mainly on molecular recognition, chiral catalysis, host-guest chemistry, and the like. Recently, the effect of the troger base skeleton in the aspects of electron transfer and push-pull is applied to novel solid fluorescent and nonlinear optical active materials, and a V-shaped rigid structure of the troger base skeleton is used for constructing a porous organic polymer. In addition, the basic nature of the troger base material in CO is due to the presence of nitrogen 2 The separation and storage aspects show great advantages. Therefore, a troger base structure is introduced into a polymer skeleton, and the troger base structure is cooperated with conjugated elements to expand to form a conjugated microporous polymer, so that hydrogen, oxygen and CO are generated by degrading and decomposing water in photocatalytic pollutants 2 Great exertion in fields of reduction conversion and the likeThe application value is high.
Example 1
The reaction equation for this example is as follows:
2.369g of diiodo troger's base (5.0mmol) is dissolved in 40mL of anhydrous N, N-dimethylformamide, and 3.344g of carbazole (20mmol), 2.764g of potassium carbonate (20mmol), 0.095g of cuprous iodide (0.5mmol) and 0.009g of 1, 10-phenanthroline (0.05mmol) are added in this order, protected with nitrogen, and reacted at 150 ℃ for 24 h. Cooling to room temperature, removing the solvent, and purifying the product by column chromatography (ethyl acetate/petroleum ether ═ 1:3) to obtain a light brown carbazolyl-based conjugated microporous polymer monomer.
0.203g (0.367mmol) of carbazolyl conjugated microporous polymer monomer is dispersed in 25mL of anhydrous chloroform, and then 0.595g (3.67mmol) of ferric chloride is added to react for 24h at 60 ℃ under the protection of nitrogen. Then, 50mL of methanol was added to the reaction mixture, and the resulting mixture was stirred for another 1 hour, and the precipitate was collected by filtration and washed with methanol, dichloromethane, and acetone in this order. The precipitate was treated with hydrochloric acid for 2 hours, filtered, and washed with water, methanol, dichloromethane, and acetone in this order. Soxhlet extraction is carried out by adopting a mixed solution of methanol and tetrahydrofuran, and purification is carried out for 24 h. And drying to obtain the earthy yellow powder conjugated microporous polymer.
FIG. 1 is an infrared spectrum of the conjugated microporous polymer prepared in example 1. Wherein the thickness is 1318cm -1 And 1060cm -1 The part is the expansion vibration absorption peak of the out-of-ring C-N, which is a carbon-nitrogen bond on a bridge connection structure in the Schlenk base structure, 1400-1720cm -1 Is a characteristic absorption peak of a benzene ring skeleton in a conjugated microporous polymer structure.
FIG. 2 is a schematic representation of the conjugated microporous polymer prepared in example 1 13 C solid nuclear magnetic spectrum. The peak position of the C-N bond on the intermediate bridging skeleton is shown at 58ppm, which indicates the existence of the troger base in the structure, and the peak position of the trisubstituent of the benzene ring structure on the carbazole is shown at 128ppm, which indicates the successful polymerization of the material.
FIG. 3 shows an embodiment1 photocatalytic CO of the conjugated microporous Polymer prepared 2 Reduction performance. Yield of 424. mu. mol g for 6h -1 h -1 。
FIG. 4 is a scanning electron micrograph of the conjugated microporous polymer prepared in example 1, and it can be seen that the microstructure is a flocculent structure.
Example 2
The reaction equation for this example is as follows:
using a mixed solution of 20ml of N, N-dimethylformamide and 20ml of triethylamine as a reaction medium, 0.356g of diiodo-cyadol base (0.75mmol), 0.075g of 1,3, 5-triethylalkynyl-benzene (0.5mmol) and 0.029g of Pd (pph) 3 ) 4 (0.025mmol) and 0.005g CuI (0.025mmol) under nitrogen at 80 ℃ for 24 h. And (3) collecting the reacted precipitate, stirring the precipitate in a hydrochloric acid solution for 1h, washing with water, stirring in a mixed solution of acetone, toluene and methanol for 1h, drying, and performing Soxhlet extraction with a mixed solution of methanol and tetrahydrofuran to obtain a yellow powdery conjugated microporous polymer.
FIG. 5 is an infrared spectrum of the conjugated microporous polymer prepared in example 2. Wherein the thickness is 1316cm -1 And 1097cm -1 The part is an expansion vibration absorption peak of the outer ring C-N, which is a carbon-nitrogen bond on a bridge connection structure in a Schlenk's base structure, 1400-1720cm -1 Is a characteristic absorption peak of a benzene ring skeleton in a conjugated microporous polymer structure, and is at 2190cm -1 The position is a characteristic peak of alkynyl in the structure.
FIG. 6 is a schematic representation of a conjugated microporous polymer prepared in example 2 13 C solid nuclear magnetic spectrum. The peak positions of C-N bonds on the intermediate bridging skeleton are shown at 57ppm and 65ppm, which indicate the existence of the vicinal alkali in the structure, and the positions of the trisubstituents of the benzene ring structure on carbazole are shown at 87 ppm.
FIG. 7 shows the photocatalytic CO of the conjugated microporous polymer prepared in example 2 2 Reduction performance. The yield of 6h was 761. mu. mol g -1 h -1 。
Example 3
The reaction equation for this example is as follows:
using a mixed solution of 20ml of N, N-dimethylformamide and 20ml of triethylamine as a reaction medium, 0.356g of diiodo-cyadol base (0.75mmol), 0.063g of 1, 4-diethynylbenzene (0.5mmol) and 0.029g of Pd (pph) 3 ) 4 (0.025mmol) and 0.005g CuI (0.025mmol) under nitrogen at 80 ℃ for 24 h. And (3) collecting the reacted precipitate, stirring the precipitate in a hydrochloric acid solution for 1h, washing with water, stirring in a mixed solution of acetone, toluene and methanol for 1h, drying, and performing Soxhlet extraction with a mixed solution of methanol and tetrahydrofuran to obtain a yellow powdery conjugated microporous polymer.
FIG. 8 is an infrared spectrum of the conjugated microporous polymer prepared in example 3. Wherein the thickness is 1316cm -1 And 1097cm -1 The part is an expansion vibration absorption peak of the outer ring C-N, which is a carbon-nitrogen bond on a bridge connection structure in a Schlenk's base structure, 1400-1720cm -1 Is a characteristic absorption peak of a benzene ring framework in a conjugated microporous polymer structure at 2190cm -1 The position is a characteristic peak of alkynyl in the structure.
FIG. 9 shows the peak positions of C-N bonds on the intermediate bridging skeleton at 57ppm and 65ppm, indicating the presence of the vicinal bases in the structure, and the position of the trisubstituents of the benzene ring structure on the carbazole at 89 ppm.
FIG. 10 is a photo-catalytic CO of the conjugated microporous polymer prepared in example 3 2 Reduction performance. The yield of 6h was 346. mu. mol g -1 h -1 。
FIG. 11 shows the UV-visible diffuse reflectance spectrum of the conjugated microporous polymer prepared in example 3, which shows good absorption at wavelengths of 200-650nm, extending to the visible region.
Claims (6)
1. A troger base-conjugated microporous polymer having the structure of formula I:
wherein, the first and the second end of the pipe are connected with each other,
is of the following structure
2. The polymer of claim 1, wherein the polymer is in the form of a powder having a pore size distribution predominantly in the range of 0.5 to 2 nm.
3. A method of making a jungel-base conjugated microporous polymer according to claim 1, comprising:
(1) a step of preparing a monomer III by using cuprous iodide as a catalyst and carrying out substitution reaction on diiodo troger base and carbazole under an alkaline condition,
(2) with FeCl 3 As a catalyst, the step of carrying out oxidative coupling self-polymerization reaction on the monomer III to prepare a target product,
4. the method of claim 3, wherein in step (1), the molar ratio of diiodo troger base to carbazole is 1: 4; the molar ratio of di-iodo troger base to cuprous iodide is 10: 1; the reaction temperature is 150 ℃, and the reaction is carried out under the protection of nitrogen.
5. The method of claim 3, wherein in step (2), the monomer is reacted with FeCl 3 In a molar ratio of 1: 10;
the reaction temperature is 60 ℃, and the reaction is carried out under the protection of nitrogen.
6. The use of the troger base conjugated microporous polymer as claimed in claim 1 in photocatalytic reduction of CO 2 The use of (1).
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