CN110330523B - Thiophene-3-formic acid-containing titanium oxide cluster monomer and preparation and application thereof - Google Patents
Thiophene-3-formic acid-containing titanium oxide cluster monomer and preparation and application thereof Download PDFInfo
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- CN110330523B CN110330523B CN201910567943.5A CN201910567943A CN110330523B CN 110330523 B CN110330523 B CN 110330523B CN 201910567943 A CN201910567943 A CN 201910567943A CN 110330523 B CN110330523 B CN 110330523B
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- 239000000178 monomer Substances 0.000 title claims abstract description 63
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 51
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- YNVOMSDITJMNET-UHFFFAOYSA-N thiophene-3-carboxylic acid Chemical compound OC(=O)C=1C=CSC=1 YNVOMSDITJMNET-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000010936 titanium Substances 0.000 claims abstract description 29
- 229920000547 conjugated polymer Polymers 0.000 claims abstract description 20
- 238000004146 energy storage Methods 0.000 claims abstract description 13
- 239000002861 polymer material Substances 0.000 claims abstract description 12
- 239000011232 storage material Substances 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 30
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 26
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 26
- 239000013078 crystal Substances 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 claims description 11
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 20
- 229920000620 organic polymer Polymers 0.000 abstract description 3
- 150000003608 titanium Chemical class 0.000 abstract description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 10
- 239000011521 glass Substances 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 5
- 229930192474 thiophene Natural products 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229920001940 conductive polymer Polymers 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000002050 diffraction method Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229920000128 polypyrrole Polymers 0.000 description 3
- 230000005611 electricity Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/28—Titanium compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/18—Definition of the polymer structure conjugated
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3222—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more oxygen atoms as the only heteroatom, e.g. furan
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Abstract
The invention discloses a thiophene-3-formic acid-containing titanium oxide cluster monomer, a preparation method thereof and application thereof in preparing an energy storage material, wherein the energy storage material is a conjugated polymer material prepared by copolymerizing the thiophene-3-formic acid-containing titanium oxide cluster monomer and a conjugated polymer monomer; the thiophene-3-formic acid-containing titanium oxygen cluster monomer C prepared by the invention40H76O16S2Ti4Can be copolymerized with common conjugated polymers to obtain a series of titanium-containing conjugated polymer materials with excellent electrochemical performance, the mass specific capacitance performance of the novel materials is improved by more than 15 percent compared with that of a pure organic polymer material, and the specific capacitance of the materials is higher than 70F/g at least.
Description
Technical Field
The invention relates to a conjugated polymer material, in particular to a novel titanium oxygen cluster monomer (C) containing thiophene-3-formic acid40H76O16S2Ti4) A preparation method thereof and application of the titanium-containing conjugated polymer material.
Background
The titanium-oxygen cluster is one of metal-oxygen clusters, the basic framework of the titanium-oxygen cluster is a cage-shaped molecular cluster which is constructed by connecting a plurality of titanium atoms through oxygen bridges, the titanium-oxygen cluster can be regarded as a nano titanium oxide material with small size and organic functional groups on the surface, and the titanium-oxygen cluster has wide application in the fields of light, electricity, catalysis and the like. The polyaniline, polypyrrole, polythiophene, poly 3, 4-ethylenedioxythiophene and other conducting polymers have good conductivity, excellent flexibility and plasticity, higher theoretical specific capacity and lower cost, and are novel materials for constructing energy storage electrode materials.
The titanium-oxygen cluster and the conductive polymer are compounded, so that the electricity storage capacity of the material can be improved, but the electron conduction efficiency and the electrochemical cycling stability of the composite material are obviously reduced due to a large number of heterogeneous interfaces among the components of the composite material. The thiophene-3-carboxylic acid-containing titanium oxide cluster monomer (C) of the present invention40H76O16S2Ti4) Can be copolymerized with conductive polymer monomers such as aniline, pyrrole, thiophene, 3, 4-ethylenedioxythiophene and the like to prepare a homogeneous conductive copolymer new material, and the new material has more excellent performances such as electrochemical cycle stability and the like compared with the conventional conductive polymer material.
Disclosure of Invention
The invention provides a novel thiophene-3-formic acid-containing titanium oxide cluster monomer and a preparation method and application thereof, wherein the titanium oxide cluster monomer and common conjugated polymer monomers such as aniline, pyrrole, thiophene, 3, 4-ethylenedioxythiophene and the like are subjected to copolymerization reaction to obtain a series of novel titanium-containing conjugated polymer materials, and the novel materials can be applied to the fields of energy storage, photoelectricity and catalysis, the influence of a branched chain containing a titanium oxide cluster in a composite material on a conjugated main chain is researched, the internal relation between the microstructure and the performance of the composite material is clarified, and the novel titanium oxide cluster monomer is a theoretical basis for designing and preparing high-performance materials.
The invention adopts the following technical scheme:
the invention provides a thiophene-3-formic acid-containing titanium oxide cluster monomer shown in a formula (I), which has a chemical formula: c40H76O16S2Ti4Molecular weight of 1067.44, molecular structural formula is shown in formula (I) in which
I.e. isopropoxy;
the invention also provides a preparation method of the thiophene-3-formic acid-containing titanium oxide cluster monomer, which comprises the following steps: hermetically mixing isopropyl titanate, thiophene-3-formic acid, cobalt bromide and an organic solvent, reacting at 60-100 ℃ (preferably 75-85 ℃) for 48-96 hours (preferably 70-80 hours), naturally cooling to room temperature, standing for crystallization, taking crystals, and drying to obtain the thiophene-3-formic acid-containing titanium dioxide cluster monomer shown in the formula (I).
Further, the organic solvent is one or more mixed solution of anhydrous isopropanol, anhydrous methanol, anhydrous ethanol, anhydrous ethyl acetate, anhydrous toluene, anhydrous acetonitrile, anhydrous dichloromethane, anhydrous trichloromethane, anhydrous carbon tetrachloride, anhydrous N, N dimethylformamide or anhydrous N-methylpyrrolidone, and preferably anhydrous acetonitrile.
Further, the mass ratio of the isopropyl titanate to the thiophene-3-carboxylic acid is 1-5: 1, preferably 3 to 4: 1, the mass ratio of the cobalt bromide to the thiophene-3-formic acid is 0.1-2: 1, preferably 0.3 to 0.8: 1. the mass ratio of the organic solvent to the thiophene-3-carboxylic acid is 50-200: 1, preferably 70-150: 1.
The invention also provides an application of the thiophene-3-formic acid-containing titanium oxide cluster monomer in preparing an energy storage material, wherein the energy storage material is a conjugated polymer material prepared by copolymerizing the thiophene-3-formic acid-containing titanium oxide cluster monomer and a conjugated polymer monomer; the conjugated polymer monomer is one or more of aniline, pyrrole, thiophene or 3, 4-ethylenedioxythiophene.
Further, the preparation method of the energy storage material comprises the following steps: dissolving the thiophene-3-formic acid-containing titanium oxygen cluster monomer and the conjugated polymer monomer in dichloromethane to prepare a titanium oxygen cluster monomer mixed solution; dissolving anhydrous ferric trichloride in nitromethane to prepare a ferric trichloride solution; dropwise adding the titanium oxide cluster monomer mixed solution into a ferric trichloride solution at 0 ℃, introducing nitrogen to carry out heat preservation reaction for 10 hours at 0 ℃, finishing the reaction, carrying out suction filtration, washing a filter cake with methanol, and drying to obtain the energy storage material. The ratio of the amount of the thiophene-3-formic acid-containing titanium oxide cluster monomer to the amount of the conjugated polymer monomer is 1:1 to 5 (preferably 1:1.0 to 2.5); the volume dosage of the dichloromethane is 50-60mL/g (preferably 57mL/g) based on the mass of the thiophene-3-formic acid-containing titanium cluster monomer; the mass ratio of the thiophene-3-formic acid-containing titanium oxide cluster monomer to the anhydrous ferric trichloride substance is 1: 10-15 (preferably 1: 14); the volume dosage of the nitromethane is 20-30mL/g (preferably 27mL/g) based on the mass of the ferric trichloride.
Compared with the prior art, the invention has the following beneficial effects: the thiophene-3-formic acid-containing titanium oxygen cluster monomer C prepared by the invention40H76O16S2Ti4Can be copolymerized with common conjugated polymers to obtain a series of titanium-containing conjugated polymer materials with excellent electrochemical performance, and the mass specific capacitance performance of the novel materials is improved by more than 15 percent compared with that of a pure organic polymer material (the specific capacitance of the material is at least more than 70F/g, and the specific capacitance of the pure organic polymer material is about 50F/g). The new material can be applied to the fields of energy storage, photoelectricity and catalysis.
Drawings
FIG. 1 shows a thiophene-3-carboxylic acid-containing titanyl cluster monomer C prepared in example 140H76O16S2Ti4A crystal photograph of (a);
FIG. 2 is C determined by X-ray single crystal diffraction analysis40H76O16S2Ti4The molecular structure of the crystal (H atom is not shown in the figure).
FIG. 3 is a diffraction analysis chart of the crystal prepared in example 1 by X-ray single crystal.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
The room temperature of the invention is 25-30 ℃.
Example 1
Adding 1mL (3.21mmol) of isopropyl titanate, 0.129g (1.01mmol) of thiophene-3-formic acid, 0.176g (0.54mmol) of cobalt bromide and 6mL (115.46mmol) of anhydrous acetonitrile into a 25mL glass bottle, sealing, mixing, placing in an oven at 80 ℃ for reaction for 72h, closing a power supply after the reaction is finished, naturally cooling to room temperature, standing for crystallization, taking crystals at 60 ℃ and drying to obtain 0.288g of thiophene-3-formic acid-containing titanium dioxide cluster monomer C40H76O16S2Ti4. The crystal photograph is shown in FIG. 1, whichThe molecular structure and the crystal structure of the crystal are determined by X-ray single crystal diffraction analysis (figure 3), and the unit cell parameters obtained by the experiment are determined as follows: (
The crystal forms are orthogonal, and the crystal space group is P212121).
Example 2
Adding 1mL (3.21mmol) of isopropyl titanate, 0.211g (1.65mmol) of thiophene-3-formic acid, 0.176g (0.54mmol) of cobalt bromide and 6mL (115.46mmol) of anhydrous acetonitrile into a 25mL glass bottle, sealing, mixing, placing in an oven at 80 ℃ for reaction for 72h, closing a power supply after the reaction is finished, naturally cooling to room temperature, standing for crystallization, taking crystals at 60 ℃ and drying to obtain 0.302g of thiophene-3-formic acid-containing titanium dioxide cluster monomer C40H76O16S2Ti4The method of example 1 was used for identification.
Example 3
Adding 1mL (3.21mmol) of isopropyl titanate, 0.083g (0.65mmol) of thiophene-3-formic acid, 0.176g (0.54mmol) of cobalt bromide and 6mL (115.46mmol) of anhydrous acetonitrile into a 25mL glass bottle, sealing, mixing, placing in an oven at 80 ℃ for reaction for 72h, turning off a power supply after the reaction is finished, naturally cooling to room temperature, standing for crystallization, taking crystals at 60 ℃ and drying to obtain 0.281g of thiophene-3-formic acid-containing titanium dioxide cluster monomer C40H76O16S2Ti4The method of example 1 was used for identification.
Example 4
Adding 1mL (3.21mmol) of isopropyl titanate, 0.129g (1.01mmol) of thiophene-3-formic acid, 0.176g (0.54mmol) of cobalt bromide and 6mL (115.46mmol) of anhydrous acetonitrile into a 25mL glass bottle, sealing, mixing, placing in a 60 ℃ oven for reaction for 72h, closing a power supply after the reaction is finished, naturally cooling to room temperature, standing for crystallization, taking crystals and drying at 60 ℃ to obtain 0.232g of thiophene-3-formic acid-containing titanium dioxide cluster monomer C40H76O16S2Ti4The method of example 1 was used for identification.
Example 5
1mL (3.21mmol) of isopropyl titanate, 0.129g (1.01mmol) of thiophene-3-carboxylic acid, 0.176g (0.54mmol) of cobalt bromide, and 6mL (115.4 mmol)6mmol) of anhydrous acetonitrile into a 25mL glass bottle, sealing and mixing, placing the mixture in a baking oven at 100 ℃ for reaction for 72 hours, turning off a power supply after the reaction is finished, naturally cooling the mixture to room temperature, standing for crystallization, taking crystals, drying the crystals at 60 ℃, and obtaining 0.269g of thiophene-3-formic acid-containing titanium dioxide cluster monomer C40H76O16S2Ti4The method of example 1 was used for identification.
Example 6
Adding 1mL (3.21mmol) of isopropyl titanate, 0.129g (1.01mmol) of thiophene-3-formic acid, 0.176g (0.54mmol) of cobalt bromide and 6mL (115.46mmol) of anhydrous acetonitrile into a 25mL glass bottle, sealing, mixing, placing in an oven at 80 ℃ for reaction for 48h, closing a power supply after the reaction is finished, naturally cooling to room temperature, standing for crystallization, taking crystals at 60 ℃ and drying to obtain 0.196g of thiophene-3-formic acid-containing titanium dioxide cluster monomer C40H76O16S2Ti4The method of example 1 was used for identification.
Example 7
Adding 1mL (3.21mmol) of isopropyl titanate, 0.129g (1.01mmol) of thiophene-3-formic acid, 0.176g (0.54mmol) of cobalt bromide and 6mL (115.46mmol) of anhydrous acetonitrile into a 25mL glass bottle, sealing, mixing, placing in an oven at 80 ℃ for reaction for 96h, closing a power supply after the reaction is finished, naturally cooling to room temperature, standing for crystallization, taking crystals at 60 ℃ and drying to obtain 0.297g of titanium dioxide cluster monomer C containing thiophene-3-formic acid40H76O16S2Ti4The method of example 1 was used for identification.
Example 8
0.7g of the titanium oxygen cluster monomer C prepared in example 140H76O16S2Ti4Dissolving 0.66mmol and 0.1g (1.47mmol) of pyrrole in 40mL of dichloromethane to prepare a titanium-oxygen cluster monomer mixed solution; 1.5g (9.25mmol) of anhydrous ferric trichloride is weighed and dissolved in 40mL of nitromethane to prepare ferric trichloride solution. And (3) placing the reaction bottle filled with the ferric trichloride solution into a low-temperature reactor, setting the temperature at 0 ℃, dropwise adding the titanium oxide cluster monomer mixed solution into the ferric trichloride solution, and introducing nitrogen to carry out heat preservation reaction for 10 hours at 0 ℃. After the reaction is finished, filtering, washing by methanol and drying to obtain the titanium-oxygen-containing cluster C40H76O16S2Ti40.543g of polypyrrole material, which can be used as a supercapacitor electrode material.
The titanium-oxygen-containing cluster C40H76O16S2Ti4Mixing, grinding and rolling the polypyrrole material, acetylene black and adhesive PTFE into an electrode sheet according to the mass ratio of 8: 1, then drying the electrode sheet in vacuum at 60 ℃, pressing the electrode sheet on a platinum sheet to prepare an electrode material, and then carrying out electrochemical test, wherein the electrolyte is LiClO of 0.1mol/L4The specific capacitance of the material is 124F/g at the current density of 1A/g.
Example 9
0.7g of the titanium oxygen cluster monomer C prepared in example 140H76O16S2Ti4Dissolving 0.66mmol of thiophene and 0.1g (1.19mmol) of thiophene in 40mL of dichloromethane to prepare a titanium-oxygen cluster monomer mixed solution; 1.5g (9.25mmol) of anhydrous ferric trichloride is weighed and dissolved in 40mL of nitromethane to prepare ferric trichloride solution. And (3) placing the reaction bottle filled with the ferric trichloride solution into a low-temperature reactor, setting the temperature at 0 ℃, dropwise adding the titanium oxide cluster monomer mixed solution into the ferric trichloride solution, and introducing nitrogen to carry out heat preservation reaction for 10 hours at 0 ℃. After the reaction is finished, the titanium-oxygen-containing cluster C is obtained by suction filtration, methanol washing and drying40H76O16S2Ti40.434g of polythiophene material. As in example 8, the specific capacitance of the material was 84F/g at a current density of 1A/g.
Example 10
0.7g of the titanium oxygen cluster monomer C prepared in example 140H76O16S2Ti4Dissolving 0.66mmol and 0.1g aniline (1.07mmol) in 40mL dichloromethane to prepare a titanium-oxygen cluster monomer mixed solution; 1.5g of anhydrous ferric trichloride (9.25mmol) was dissolved in 40mL of nitromethane to prepare a ferric trichloride solution. And (3) placing the reaction bottle filled with the ferric trichloride solution into a low-temperature reactor, setting the temperature to be 0 ℃, dropwise adding the titanium oxide cluster monomer mixed solution into the ferric trichloride solution, introducing nitrogen at the temperature of 0 ℃, and carrying out heat preservation reaction for 10 hours. After the reaction is finished, the titanium-oxygen-containing cluster C is obtained by suction filtration, methanol washing and drying40H76O16S2Ti40.651g of the polyaniline material. As in example 8, the specific capacitance of the material was 140F/g at a current density of 1A/g.
Example 11
0.7g of the titanium oxygen cluster monomer C prepared in example 140H76O16S2Ti4Dissolving 0.66mmol and 0.1g (0.70mmol) of 3, 4-ethylene dioxythiophene in 40mL of dichloromethane to prepare a monomer mixed solution of the titanium oxide cluster compound; 1.5g (9.25mmol) of anhydrous ferric trichloride is weighed and dissolved in 40mL of nitromethane to prepare ferric trichloride solution. And (3) placing the reaction bottle filled with the ferric trichloride solution into a low-temperature reactor, setting the temperature to be 0 ℃, dropwise adding the titanium oxide cluster monomer mixed solution into the ferric trichloride solution, introducing nitrogen at the temperature of 0 ℃, and carrying out heat preservation reaction for 10 hours. After the reaction is finished, the titanium-oxygen-containing cluster C is obtained by suction filtration, methanol washing and drying40H76O16S2Ti40.379g of poly (3, 4-ethylenedioxythiophene) material. As in example 8, the specific capacitance of the material was 77F/g at a current density of 1A/g.
Claims (7)
1. The application of the thiophene-3-formic acid-containing titanium oxide cluster monomer shown in the formula (I) in preparing an energy storage material is characterized in that the energy storage material is a conjugated polymer material prepared by copolymerizing the titanium oxide cluster monomer and a conjugated polymer monomer; the conjugated polymer monomer is one or more of aniline and pyrrole;
（Ⅰ）
in the formula (I) i PrO is isopropoxy.
2. The use of claim 1, wherein the titanyl cluster monomer is prepared by a process comprising: hermetically mixing isopropyl titanate, thiophene-3-formic acid, cobalt bromide and an organic solvent, reacting at 60-100 ℃ for 48-96 hours, naturally cooling to room temperature, standing for crystallization, taking crystals and drying to obtain the thiophene-3-formic acid-containing titanium dioxide cluster monomer shown in the formula (I).
3. Use according to claim 2, characterized in that: the mass ratio of isopropyl titanate to thiophene-3-formic acid is 1-5: 1; the mass ratio of the cobalt bromide to the thiophene-3-formic acid is 0.1-2: 1.
4. use according to claim 2, characterized in that: the organic solvent is one or more mixed solution of anhydrous isopropanol, anhydrous methanol, anhydrous ethanol, anhydrous ethyl acetate, anhydrous toluene, anhydrous acetonitrile, anhydrous dichloromethane, anhydrous trichloromethane, anhydrous carbon tetrachloride, anhydrous N, N dimethylformamide or anhydrous N-methylpyrrolidone.
5. Use according to claim 2, characterized in that: the mass ratio of the organic solvent to the thiophene-3-formic acid is 50-200: 1.
6. The use according to claim 1, wherein the energy storage material is prepared by a method comprising: dissolving the titanium oxygen cluster compound monomer and the conjugated polymer monomer in dichloromethane to prepare a titanium oxygen cluster monomer mixed solution; dissolving anhydrous ferric trichloride in nitromethane to prepare a ferric trichloride solution; dropwise adding the titanium oxide cluster monomer mixed solution into a ferric trichloride solution at 0 ℃, introducing nitrogen to carry out heat preservation reaction for 10 hours at 0 ℃, finishing the reaction, carrying out suction filtration, washing a filter cake with methanol, and drying to obtain the energy storage material.
7. The use of claim 6, wherein the ratio of the amount of said titanium oxo cluster monomer to conjugated polymer monomer species is 1:1 to 5; the volume usage of the dichloromethane is 50-60mL/g calculated by the mass of the titanium oxide cluster monomer; the quantity ratio of the titanium oxygen cluster monomer to the anhydrous ferric trichloride substance is 1: 10-15; the volume dosage of the nitromethane is 20-30mL/g based on the mass of the ferric trichloride.
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Application publication date: 20191015 Assignee: Hubei Tujia Old Liquor Industry Co.,Ltd. Assignor: JIANG University OF TECHNOLOGY Contract record no.: X2023980035406 Denomination of invention: A titanium oxide cluster monomer containing thiophene-3-carboxylic acid and its preparation and application Granted publication date: 20211119 License type: Common License Record date: 20230515 |