CN111793065A - Spirocyclic aromatic organic conjugated micromolecular thermoelectric material and preparation and application thereof - Google Patents
Spirocyclic aromatic organic conjugated micromolecular thermoelectric material and preparation and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 125000003118 aryl group Chemical group 0.000 title description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 17
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 14
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 10
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- 238000006243 chemical reaction Methods 0.000 claims description 36
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 20
- 150000003384 small molecules Chemical class 0.000 claims description 15
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 14
- -1 spiro aromatic hydrocarbon Chemical class 0.000 claims description 13
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 12
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [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 claims description 12
- 239000010409 thin film Substances 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
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- 239000003054 catalyst Substances 0.000 claims description 7
- 229940125782 compound 2 Drugs 0.000 claims description 7
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- 238000002156 mixing Methods 0.000 claims description 6
- 238000006265 spirocyclization reaction Methods 0.000 claims description 6
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- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 5
- 239000006184 cosolvent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910003472 fullerene Inorganic materials 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical group [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 239000013067 intermediate product Substances 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 238000004440 column chromatography Methods 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000012074 organic phase Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 2
- BPLUKJNHPBNVQL-UHFFFAOYSA-N triphenylarsine Chemical compound C1=CC=CC=C1[As](C=1C=CC=CC=1)C1=CC=CC=C1 BPLUKJNHPBNVQL-UHFFFAOYSA-N 0.000 claims description 2
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 claims 1
- 125000003003 spiro group Chemical group 0.000 abstract description 22
- 230000005540 biological transmission Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 238000004770 highest occupied molecular orbital Methods 0.000 abstract description 5
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 abstract description 5
- 238000009825 accumulation Methods 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 125000001424 substituent group Chemical group 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- 239000002109 single walled nanotube Substances 0.000 description 19
- 239000010408 film Substances 0.000 description 13
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
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- 239000007864 aqueous solution Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- CWGRCRZFJOXQFV-UHFFFAOYSA-N 2,7-dibromofluoren-9-one Chemical compound C1=C(Br)C=C2C(=O)C3=CC(Br)=CC=C3C2=C1 CWGRCRZFJOXQFV-UHFFFAOYSA-N 0.000 description 2
- FFZHICFAHSDFKZ-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-thiophen-2-yl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=CS1 FFZHICFAHSDFKZ-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
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- QQNLHOMPVNTETJ-UHFFFAOYSA-N spiro[fluorene-9,9'-xanthene] Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11C2=CC=CC=C2C2=CC=CC=C21 QQNLHOMPVNTETJ-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000005676 thermoelectric effect Effects 0.000 description 2
- HPOQARMSOPOZMW-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-(5-thiophen-2-ylthiophen-2-yl)-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(C=2SC=CC=2)S1 HPOQARMSOPOZMW-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 101100299498 Xenopus laevis pteg gene Proteins 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 239000002048 multi walled nanotube Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- FHCPAXDKURNIOZ-UHFFFAOYSA-N tetrathiafulvalene Chemical class S1C=CSC1=C1SC=CS1 FHCPAXDKURNIOZ-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/856—Thermoelectric active materials comprising organic compositions
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses a spiro aromatic organic conjugated micromolecule thermoelectric material and preparation and application thereof; the structural general formula of the thermoelectric material is
Wherein R is selected from
R' is selected from H,
And R' are not simultaneously
n is an integer, and n is more than or equal to 0 and less than or equal to 5. The thermoelectric material developed and designed by the invention has a spiral conjugated structure with a vertical space configuration; the spiro conjugated structure can increase the charge transmission capability of a three-dimensional space through a charge hopping process, effectively increase the charge transmission effect between the thermoelectric material and an inorganic carbon material (such as a carbon nano tube), and improve the conductivity of a composite material formed by compounding the thermoelectric material and the inorganic carbon material; the spiro conjugated structure enables the thermoelectric material of the invention to have moderate solubility, and intermolecular accumulation, HOMO and LUMO electronic energy levels and energy gaps of the thermoelectric material of the invention can be regulated and controlled by modifying side chain substituents of the spiro conjugated structure, thereby playing a role in optimizing thermoelectric performance.
Description
Technical Field
The invention relates to the technical field of thermoelectric materials, in particular to a spiro-aromatic organic conjugated micromolecule thermoelectric material and preparation and application thereof.
Background
The energy crisis and the greenhouse effect are one of the focus problems in the world, and the effective utilization of energy is crucial in the background of the exhaustion of fossil energy, however, most of the heat energy generated in the human industry and daily life is wasted in a diffusion form. In this context, thermoelectric technology, which is the simplest technology capable of realizing direct interconversion between thermal energy and electric energy, has become one of the international important research hotspots in recent years. Thermoelectric materials can convert solar energy, geothermal energy, automobile and industrial waste heat into electricity, and conversely, the electricity can be used as a heat pump to realize refrigeration, and at present, the commercial application of thermoelectric materials mainly focuses on thermocouple temperature control and semiconductor refrigeration. The thermoelectric effect is found for more than 100 years, but the application of the thermoelectric effect in power generation, refrigeration, heat pumps and the like still cannot realize large-scale commercialization, and the main reason is that the conversion efficiency and the refrigeration efficiency of thermoelectric materials are low and cannot compete with the existing commercialized power generation and refrigeration modes.
At present, the research and development technology of inorganic thermoelectric materials is mature day by day, and part of the research and development technology even realizes commercialization, such as providing electric power for field exploration and travel, developing the constant temperature technology of automobile seats and the like. However, these materials have disadvantages of high thermal conductivity, toxicity, high cost, difficulty in processing, etc., which have hindered their further development. Compared with inorganic thermoelectric materials, organic thermoelectric materials have low thermal conductivity, are easy to process and synthesize, have low cost, abundant resources, are environment-friendly, and have the advantages of flexibility, lightness and large-area manufacturing, and are receiving attention. At present, researches on organic thermoelectric materials mainly focus on pi-conjugated polymer molecules, but researches on organic small-molecule thermoelectric materials which have definite molecular structures, high purity, adjustable molecular sizes and easy derivatization are few, and the organic small-molecule thermoelectric materials are mainly limited to a plurality of limited organic small-molecule compounds such as pentacene and tetrathiafulvalene derivatives, and the performance indexes of the small-molecule thermoelectric materials are far lower than those of high-molecular thermoelectric materials. Therefore, the development of novel high-efficiency organic small-molecule thermoelectric materials and devices based on the same have great research significance and value.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a spiro aromatic hydrocarbon organic conjugated micromolecule thermoelectric material, and preparation and application thereof, and aims to solve the problem that the prior organic micromolecule thermoelectric material has poor performances such as thermoelectric conversion efficiency and the like.
The technical scheme of the invention is as follows:
in a first aspect, the invention provides a spiro aromatic hydrocarbon organic conjugated micromolecule thermoelectric material, and the structural general formula of the thermoelectric material is shown in the specification
Wherein R is selected from
Or
R' is selected from H,
And R' are not simultaneously
n is an integer, and n is more than or equal to 0 and less than or equal to 5.
In a second aspect, the present invention provides a method for preparing the spiro aromatic hydrocarbon organic conjugated small molecule thermoelectric material, wherein the method is according to the reaction formula (1)
The method comprises the following steps:
A. in an inert atmosphere, mixing halogenated fluorenone 1, a naphthol compound 2 and methanesulfonic acid, carrying out a spiro cyclization reaction, and purifying after the reaction is finished to obtain an intermediate product 3;
wherein the halogenated fluorenone 1 is
The naphthol compound 2 is
Intermediate 3 is
X is Cl, Br or I, R' is H,
n is an integer, and n is more than or equal to 0 and less than or equal to 5;
B. in an inert atmosphere, inorganic base, Pd (0) catalyst, intermediate 3,
Mixing the thermoelectric material with a cosolvent, carrying out Suzuki reaction, quenching the reaction after the reaction is completed, and purifying to obtain the thermoelectric material;
wherein R is selected from
R and R' are not simultaneously
In a third aspect, the present invention provides a thermoelectric thin film, the material of which comprises the thermoelectric material as described above.
In a fourth aspect, the present invention provides a thermoelectric device comprising a thermoelectric thin film as described above.
Has the advantages that: the space stereo organic conjugated small molecule thermoelectric material with the spiro structure uses the spiro conjugated structure with the vertical structure of the spirofluorene-anthracene (spiro [ fluorene-9,9' -xanthene ]) as the core molecular skeleton in the thermoelectric material system, and the spiro structure has sp3 carbon, so that two orthogonal pi systems are connected together, and the thermoelectric material has the conjugated structure in the three-dimensional space. The spiro aromatic organic conjugated micromolecules are compounded with inorganic carbon materials (such as carbon nano tubes, fullerene or graphene), and the charge transmission capability of a three-dimensional space can be increased through a charge hopping process due to the spiro structure, so that the charge transmission effect between the spiro aromatic molecules and the inorganic carbon materials is increased, and the conductivity of the composite material is improved. Meanwhile, the spiro structure with the vertical space configuration also has certain solubility, and modification of side chain substituents of the spiro structure can regulate and control intermolecular accumulation, and can play a role in regulating and controlling the electron energy level and energy gap of a Highest Occupied Molecular Orbital (HOMO) and a Lowest Unoccupied Molecular Orbital (LUMO), thereby playing a role in optimizing thermoelectric performance.
Drawings
Fig. 1 is a three-dimensional structure model of Spiro-1 in xy plane (a) and yz plane (b) in the embodiment of the present invention.
FIG. 2 is a graph showing the thermoelectric properties of the composite material Spiro-1/SWCNT according to the weight content of Spiro-1 in example 4 of the present invention.
FIG. 3 is a graph showing the thermoelectric properties of the composite material Spiro-2/SWCNT according to the weight content of Spiro-2 in example 5 of the present invention.
Detailed Description
The invention provides a spiro aromatic organic conjugated micromolecule thermoelectric material and preparation and application thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The organic thermoelectric material has ultra-low thermal conductivity and becomes a hot spot in the thermoelectric research field, but the research progress of the organic thermoelectric material is greatly hindered by the lower electrical conductivity.
Based on the structure, the invention provides the spiro aromatic hydrocarbon organic conjugated micromolecule thermoelectric material, wherein the structural general formula of the thermoelectric material is shown in the specification
Wherein R is selected from
R' is selected from H,
And R' are not simultaneously
n is an integer, and n is more than or equal to 0 and less than or equal to 5.
In this embodiment, the spatial stereo organic conjugated small molecule thermoelectric material with a spiro structure uses a spiro conjugated structure with a vertical structure of spirofluorene-anthracene (spiro-9, 9' -xanthene) as a core molecular skeleton in a thermoelectric material system, and the spiro structure has sp3 carbon, so that two orthogonal pi systems are connected together, and the thermoelectric material has a conjugated structure in a three-dimensional space. The spiro aromatic organic conjugated micromolecules are compounded with inorganic carbon materials (such as carbon nano tubes, fullerene or graphene), and the charge transmission capability of a three-dimensional space can be increased through a charge hopping process due to the spiro structure, so that the charge transmission effect between the spiro aromatic molecules and the inorganic carbon materials is increased, and the conductivity of the composite material is improved. Meanwhile, the spiro structure with the vertical space configuration also has certain solubility, and modification of side chain substituents of the spiro structure can regulate intermolecular accumulation and can play a role in regulating electronic energy levels and energy gaps of HOMO and LUMO, so that optimization of thermoelectric performance is realized.
It should be noted that, in the following description,
curve key of (1)
The position is R, R'.
Specifically, referring to FIG. 1, a representative spirocyclic aromatic hydrocarbon conjugated organic small molecule Spiro-1 (structure is
) As can be seen from the three-dimensional structural models of the xy plane (b) and the yz plane (c), the core molecular skeleton (spirofluorene-anthracene) of the spirocyclic aromatic conjugated organic small molecule of the present embodiment(spiro[fluorene-9,9'-xanthene]) A spiro conjugated structure with a vertical structure), which has sp3 carbon, and the sp3 carbon connects two orthogonal pi systems together, so that the spiro aromatic hydrocarbon conjugated organic small molecule thermoelectric material of the present embodiment has a conjugated structure in three-dimensional space. On one hand, the spiro conjugated structure with the vertical space configuration can increase the charge transmission capability of a three-dimensional space through a charge hopping process, so that when the spiro aromatic hydrocarbon organic conjugated micromolecule thermoelectric material is compounded with inorganic carbon materials such as carbon nano tubes, fullerene or graphene, the spiro conjugated structure with the vertical space configuration can effectively increase the charge transmission effect between the spiro molecule and the inorganic carbon materials, and the electrical conductivity of the composite material is improved; on the other hand, the spiro conjugated structure with the vertical space configuration also has certain solubility, and modification of side chain substituents of the spiro conjugated structure can regulate and control intermolecular accumulation, and can play a role in regulating and controlling electronic energy levels and energy gaps of HOMO and LUMO, thereby playing a role in optimizing thermoelectric performance.
In one embodiment, the thermoelectric material is
The invention provides a preparation method of the spiro aromatic hydrocarbon organic conjugated micromolecule thermoelectric material, wherein the preparation method is according to the reaction formula (1)
The method comprises the following steps:
A. in an inert atmosphere, mixing halogenated fluorenone 1, a naphthol compound 2 and methanesulfonic acid, carrying out a spiro cyclization reaction, and purifying after the reaction is finished to obtain an intermediate product 3;
wherein the halogenated fluorenone 1 is
The naphthol compound 2 is
Intermediate 3 is
X is Cl, Br or I, R' is H,
n is an integer, and n is more than or equal to 0 and less than or equal to 5;
B. in an inert atmosphere, inorganic base, Pd (0) catalyst, intermediate 3,
Mixing the thermoelectric material with a cosolvent, carrying out Suzuki reaction, quenching the reaction after the reaction is completed, and purifying to obtain the thermoelectric material;
wherein R is selected from
R and R' are not simultaneously
It should be noted that, in the following description,
curve key of (1)
The position is R, R'.
In one embodiment, in step a, the cosolvent is a mixed solvent of ethylene glycol dimethyl ether (DME) and water; further, the volume ratio of the ethylene glycol dimethyl ether to water is 3-2: 1; preferably, the volume ratio of ethylene glycol dimethyl ether to water is 2: 1. The temperature of the spiro cyclization reaction is 140-160 ℃, and preferably 150 ℃. The spiro cyclization reaction time is 18-24 hours, and preferably 24 hours. The molar ratio of the halogenated fluorenone 1 to the naphthol compound 2 to the methanesulfonic acid is 1: 2.5-5: 2.5-5; preferably in a molar ratio of 1:4: 4.
In one embodiment, in step B, the inorganic base may be selected from, but is not limited to, Cs2CO3、K2CO3、Na2CO3Or Li2CO3One or more of; preferably, the inorganic base is K2CO3. The Pd (0) catalyst may be selected from, but is not limited to, tetrakis (triphenylphosphine) palladium (0) (Pd (PPh)3)4) Tetrakis (triphenylarsine) palladium (0) (Pd (AsPh)3)4) Tetrakis (tri-n-butylphosphine) palladium (0) (Pd (n-Bu)3P)4) And tetrakis (trimethoxyphosphine) palladium (0) (Pd [ (MeO)3P]4) One or more of; preferably, the Pd (0) catalyst is tetrakis (triphenylphosphine) palladium (0). The temperature of the Suzuki reaction is 80-100 ℃, and preferably 80 ℃. The time is 18-24 h, preferably 24 h. The intermediate product 3, inorganic base, Pd (0) catalyst,
In a molar ratio of 1: 3-5: 0.01-0.15: 3-5; the preferred molar ratio is 1: 5:0.1:4.
In one embodiment, the inert atmosphere is a nitrogen atmosphere or an argon atmosphere. The purification may include: extracting, drying organic phase, removing solvent, and separating by column chromatography.
The present invention provides a thermoelectric thin film, the material of which comprises the thermoelectric material as described above.
In one embodiment, the material of the thermoelectric thin film is a composite material of the thermoelectric material and an inorganic carbon material, and the weight content of the thermoelectric material in the composite material is 10-90 wt%.
In one embodiment, the inorganic carbon material may be selected from, but is not limited to, one or more of carbon nanotubes, fullerenes, and graphene, such as single-walled carbon nanotubes, multi-walled carbon nanotubes, and the like.
The invention also provides a thermoelectric device, wherein the thermoelectric device comprises the thermoelectric thin film as described in any one of the above.
The present invention will be described in detail below with reference to specific examples.
Example 1 preparation of thermoelectric Material Spiro-1
(1) According to the reaction formula (2)
Intermediate 3-1-1 was prepared according to the following procedure:
1mmol of 2, 7-dibromo-9-fluorenone and 4mmol of 1-naphthol are mixed, 4mmol of methanesulfonic acid is added to the mixture, and then stirring is carried out at 150 ℃ for 24 hours under the protection of inert gas. After the reaction was completed, the reaction was quenched by adding an appropriate amount of water and extracted with dichloromethane, dried over anhydrous magnesium sulfate, and then the solvent was removed by rotary evaporation, and the resulting residue was purified by silica gel column chromatography using petroleum ether/ethyl acetate (volume ratio 20:1) as an eluent to give 518mg of the product 3-1-1 as a white solid in a yield of about 80%.
(2) According to the reaction formula (3)
Spiro-1 was prepared according to the following procedure:
in N2Under the protection of (1), 0.2mmol of the compound 3-1-1 and 0.8mmol of thiophene-2-boronic acid pinacol ester are mixed, 10mL of ethylene glycol dimethyl ether and 5mL of 2M potassium carbonate aqueous solution are added, the mixed solution is subjected to bubbling under inert gas to remove oxygen for 15min, and then Pd (PPh) is added3)4(10% eq., 0.02mmol), the reaction was stirred continuously at 80 ℃ for 24h, and the reaction was monitored by Thin Layer Chromatography (TLC) plates. After the reaction is completed, adding water to quench the reaction, extracting with dichloromethane, drying with anhydrous magnesium sulfate, removing the solvent by rotary evaporation, and purifying the obtained residue by silica gel column chromatography with petroleum ether/dichloromethane (volume ratio is 10:1) as an eluent to obtain 100mg of white solid product, namely, Spiro-1, with the yield of 84%; for measuring Spiro-11H NMR(600MHz,CDCl3)8.86(d, J ═ 8.4Hz,2H),7.89(d, J ═ 8.0Hz,2H),7.80(d, J ═ 8.0Hz,2H),7.76(td, J ═ 7.0Hz,1.0Hz,2H),7.71(dd, J ═ 8.0Hz,1.7Hz,2H),7.62-7.58(m,2H),7.40(d, J ═ 1.4Hz,2H),7.32(d, J ═ 8.6Hz,2H),7.17(d, J ═ 4.4Hz,4H),6.95(t, J ═ 4.2Hz,2H),6.53(d, J ═ 6.2Hz, 2H). It is composed of13C NMR(150MHz,CDCl3)157.03,145.76,144.05,138.70,134.73,133.62,127.90,127.70,126.70,126.28,126.14,125.66,124.77,124.60,123.55,123.35,123.30,121.74,120.40,117.59,54.40。
Example 2 preparation of thermoelectric Material Spiro-2
According to the reaction formula (4)
Spiro-2 was prepared according to the following procedure:
in N2Under the protection of (1), 0.2mmol of the compound 3-1-1 is mixed with 0.8mmol of 2,2' -bithiophene-5-boronic acid pinacol ester, 10mL of ethylene glycol dimethyl ether and 5mL of 2M potassium carbonate aqueous solution are added, the mixed solution is bubbled under inert gas to remove oxygen for 15 minutes, and then Pd (PPh) is added3)4(10% eq., 0.02mmol), the reaction was stirred continuously at 80 ℃ for 24h, and the reaction was monitored by TLC plates. After the reaction was completed, the reaction was quenched with water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation, and the obtained residue was purified by silica gel column chromatography using petroleum ether/dichloromethane (volume ratio: 10:1) as an eluent to give 100mg of a yellow solid product, Spiro-2, in 66% yield, of Spiro-21H NMR(500MHz,CDCl3)8.87(d,J＝10.5Hz,2H),7.89(d,J＝10.0Hz,2H),7.82-7.75(m,4H),7.69(dd,J＝10.0Hz,1.6Hz,2H),7.61(t,J＝9.3Hz,2H),7.39-7.32(m,4H),7.17(d,J＝6.2Hz,2H),7.10(dd,J＝12Hz,4.1Hz,4H),7.02(d,J＝4.8Hz,2H),6.97(dd,J＝10.0Hz,4.9Hz,2H),6.54(d,J＝10.8Hz,2H)。13C NMR(125MHz,CDCl3)157.17,145.77,142.68,138.77,137.34,136.71,134.42,133.68,127.81,127.75,126.76,126.34,125.79,125.64,124.64,124.46,124.32,124.02,123.55,123.40,123.18,121.77,120.50,117.46,54.41。
Example 3 preparation of thermoelectric Material Spiro-3
(1) According to reaction formula (5)
Intermediate 3-3-1 was prepared according to the following procedure:
1mmol of 2, 7-dibromo-9-fluorenone was mixed with 4mmol of phenol, and 4mmol of methanesulfonic acid was added to the mixture, followed by stirring at 150 ℃ for 24 hours under an inert gas atmosphere. After the reaction was completed, the reaction was quenched by adding an appropriate amount of water and extracted with dichloromethane, dried over anhydrous magnesium sulfate, and then the solvent was removed by rotary evaporation, and the obtained residue was purified by silica gel column chromatography using petroleum ether/ethyl acetate (volume ratio: 10:1) as an eluent to obtain 382mg of a white solid product 3-3-1 in about 78% yield.
(2) According to reaction formula (6)
Spiro-3 was prepared according to the following procedure:
in N2Under the protection of (1), 0.4mmol of the compound 3-3-1 and 1.6mmol of thiophene-2-boronic acid pinacol ester are mixed, 20mL of ethylene glycol dimethyl ether and 10mL of 2M sodium carbonate aqueous solution are added, the mixed solution is subjected to bubbling under inert gas to remove oxygen for 15 minutes, and then Pd (PPh) is added3)4(10% eq., 0.04mmol), the reaction was stirred continuously at 80 ℃ for 24h, and the reaction was monitored by TLC plate. After the reaction was completed, water was added to quench the reaction, dichloromethane was extracted, anhydrous magnesium sulfate was dried, the solvent was removed by rotary evaporation, and the obtained residue was purified by silica gel column chromatography using petroleum ether/dichloromethane (volume ratio: 10:1) as an eluent to give 127.5mg of white solid product, Spiro-3, yield 64%, and measured value of Spiro-31H NMR(500MHz,CDCl3)7.78(d,J＝8.0Hz,2H),7.63(dd,J＝8.0Hz,1.5Hz,2H),7.38(d,J＝1.1Hz,2H),7.27-7.19(m,8H),6.97(dd,J＝5.0Hz,3.7Hz,2H),6.81-6.78(m,2H),6.50(dd,J＝7.8Hz,1.2Hz,2H)。13C NMR(125MHz,CDCl3)156.03,151.36,144.24,138.58,134.62,128.33,128.07,127.99,126.00,124.83,124.46,123.51,123.34,122.97,120.41,116.91,54.38。
Example 4 preparation and Performance testing of Spiro-1 based thermoelectric films
(1) 8mg of single-walled carbon nanotubes (SWCNT) and 8mL of chlorobenzene were sonicated in a 25mL round bottom flask for 4h followed by magnetic stirring for 24h to give a uniform SWCNT dispersion. 10mg of Spiro-1 was weighed out and completely dissolved in 10mL of chlorobenzene to prepare a Spiro-1 solution having a concentration of 10 mg/mL. The SWCNT dispersion and the Spiro-1 solution are mixed in a certain ratio to prepare a Spiro-1/SWCNT composite solution with the weight contents of Spiro-1 (based on the weight of Spiro-1/SWCNT) of 10 wt%, 30 wt%, 50 wt%, 70 wt% and 90 wt%.
(2) And dripping the Spiro-1/SWCNT composite material solution onto a glass sheet in a dripping mode, and naturally drying the solvent to form the thermoelectric film. The results of the test of the electrical conductivity, seebeck coefficient and power factor of the thermoelectric thin film based on the Spiro-1 are shown in fig. 2, and it can be seen that: wherein when the weight content of the molecule Spiro-1 is 0 wt%, the Power Factor (PF) of the thermoelectric film is 156.7 μ W.m-1K-2(ii) a When the weight content of the small molecule Spiro-1 is 30 wt%, the electric Conductivity (sigma) of the thermoelectric film is highest and reaches 631.6 S.m-1(ii) a The seebeck coefficient (S) of the thermoelectric film generally steadily increased with increasing small molecule Spiro-1 content; the power factor reaches a nearly maximum value of 215.3 μ W.m at a weight content of 40-60 wt%-1K-2。
Example 5 preparation and Performance testing of Spiro-2 based thermoelectric films
(1) 8mg of single-walled carbon nanotubes (SWCNT) and 8mL of chlorobenzene were sonicated in a 25mL round bottom flask for 4h followed by magnetic stirring for 24h to give a uniform SWCNT dispersion. 10mg of Spiro-2 was weighed out and completely dissolved in 10mL of chlorobenzene to prepare a Spiro-2 solution having a concentration of 10 mg/mL. The SWCNT dispersion and the Spiro-2 solution are mixed in a certain ratio to prepare a Spiro-2/SWCNT composite solution with the weight contents of Spiro-2 (based on the weight of Spiro-2/SWCNT) of 10 wt%, 30 wt%, 50 wt%, 70 wt% and 90 wt%.
(2) And dripping the Spiro-2/SWCNT composite material solution onto a glass sheet in a dripping mode, and naturally drying the solvent to form the thermoelectric film. The results of the tests of the electrical conductivity, seebeck coefficient and power factor of the thermoelectric thin film based on the Spiro-2 are shown in fig. 3: wherein when the weight content of Spiro-2 is 0 wt%, the Power Factor (PF) of the thermoelectric film is 148.72 mu W m-1K-2(ii) a When the weight content of Spiro-2 is 10 wt%, the electric conductivity (sigma) of the thermoelectric film is highest and reaches 555.1S m-1(ii) a The Seebeck Coefficient (S) of the thermoelectric film generally steadily increases with increasing weight content of small molecule Spiro-2; the power factor reaches a near maximum at a Spiro-2 content of 30 wt%, 177.1 μ W.m-1K-2。
Example 6 comparative analysis of the Performance of a thermoelectric film based on Spiro and a thermoelectric film based on a conventional organic thermoelectric Material
Thermoelectric properties (maximum power factor PF) of the thermoelectric composite materials Spiro-1/SWCNT and Spiro-2/SWCNT measured in examples 4 and 5 respectivelymaxElectric conductivity sigma and Seebeck coefficient S corresponding to the electric conductivity sigma) and thermoelectric property (maximum power factor PF) of thermoelectric material formed by compounding organic micromolecules or macromolecules and carbon nano tubes reported at presentmaxAnd the film conductivity σ and seebeck coefficient S) corresponding thereto are shown in table 1. It can be seen that the thermoelectric performance of the composite material based on the novel Spiro-structured small molecule Spiro is superior to that of the composite material formed by compounding the reported organic thermoelectric material with carbon nanotubes.
TABLE 1
[ note ]: the structural formulas of CuPc, TPNO, TCzPy, PANiPy and PTEG are respectively
In conclusion, the invention provides the spiro aromatic hydrocarbon organic conjugated micromolecule thermoelectric material and the preparation and the application thereof, and the spiro aromatic hydrocarbon organic conjugated micromolecule developed and designed by the invention has a special three-dimensional conjugated structure and is a good organic thermoelectric material. The inorganic carbon material (such as carbon nano tube) is physically compounded, the three-dimensional conjugated structure increases the interaction between organic molecules and the inorganic carbon material (such as carbon nano tube), higher thermoelectric performance can be obtained, high-efficiency thermoelectric conversion efficiency is realized, and the method is favorable for large-scale application in the thermoelectric field.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. The spiro aromatic hydrocarbon organic conjugated micromolecule thermoelectric material is characterized in that the structural general formula of the thermoelectric material is shown in the specification
Wherein R is selected from
R' is selected from H,
And R andr' is not simultaneously
n is an integer, and n is more than or equal to 0 and less than or equal to 5.
2. The spiro aromatic hydrocarbon organic conjugated small molecule thermoelectric material as claimed in claim 1, wherein the thermoelectric material is selected from the group consisting of
3. A method for preparing a spiro aromatic hydrocarbon organic conjugated small molecule thermoelectric material as claimed in claim 1 or 2, characterized in that according to the reaction formula (1)
The method comprises the following steps:
A. in an inert atmosphere, mixing halogenated fluorenone 1, a naphthol compound 2 and methanesulfonic acid, carrying out a spiro cyclization reaction, and purifying after the reaction is finished to obtain an intermediate product 3;
wherein the halogenated fluorenone 1 is
The naphthol compound 2 is
Intermediate 3 is
X is Cl, Br or I, R' is H,
n is an integer, and n is more than or equal to 0 and less than or equal to 5;
B. in an inert atmosphere, inorganic base, Pd (0) catalyst, intermediate 3,
Mixing the thermoelectric material with a cosolvent, carrying out Suzuki reaction, quenching the reaction after the reaction is completed, and purifying to obtain the thermoelectric material;
wherein R is selected from
R and R' are not simultaneously
4. The preparation method according to claim 3, wherein in the step A, the cosolvent is a mixed solvent of ethylene glycol dimethyl ether and water;
the temperature of the spiro cyclization reaction is 140-160 ℃, and the time is 18-24 h.
5. The process according to claim 3, wherein in step B, the inorganic base is selected from Cs2CO3、K2CO3、Na2CO3Or Li2CO3One or more of;
the Pd (0) catalyst is selected from one or more of tetrakis (triphenylphosphine) palladium (0), tetrakis (triphenylarsine) palladium (0), tetrakis (tri-n-butylphosphine) palladium (0) and tetrakis (trimethoxyphosphine) palladium (0);
the temperature of the Suzuki reaction is 80-100 ℃, and the time is 18-24 h.
6. The production method according to claim 3, wherein the inert atmosphere is a nitrogen atmosphere or an argon atmosphere;
the purification comprises the following steps: extracting, drying organic phase, removing solvent, and separating by column chromatography.
7. A thermoelectric thin film characterized in that a material of the thermoelectric thin film comprises the thermoelectric material according to claim 1 or 2.
8. The thermoelectric thin film according to claim 7, wherein a material of the thermoelectric thin film is a composite material of the thermoelectric material and an inorganic carbon material, and a weight content of the thermoelectric material in the composite material is 10 to 90 wt%.
9. The thermoelectric material according to claim 8, wherein the inorganic carbon material is selected from one or more of carbon nanotubes, fullerenes, and graphene.
10. A thermoelectric device comprising the thermoelectric thin film according to any one of claims 7 to 9.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101440082A (en) * | 2008-12-12 | 2009-05-27 | 南京邮电大学 | Spirofluorene xanthene material, and preparation and use thereof |
| CN106165132A (en) * | 2014-02-28 | 2016-11-23 | 国立大学法人奈良先端科学技术大学院大学 | Thermo-electric converting material and thermoelectric conversion element |
| CN109880063A (en) * | 2019-02-21 | 2019-06-14 | 深圳大学 | Conjugated polymer and preparation method and application based on benzene thiophene unit |
| US20200062740A1 (en) * | 2018-08-23 | 2020-02-27 | Purdue Research Foundation | Thiophene monoamine based organic-inorganic hybrid perovskites |
-
2020
- 2020-07-31 CN CN202010761919.8A patent/CN111793065B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101440082A (en) * | 2008-12-12 | 2009-05-27 | 南京邮电大学 | Spirofluorene xanthene material, and preparation and use thereof |
| CN106165132A (en) * | 2014-02-28 | 2016-11-23 | 国立大学法人奈良先端科学技术大学院大学 | Thermo-electric converting material and thermoelectric conversion element |
| US20200062740A1 (en) * | 2018-08-23 | 2020-02-27 | Purdue Research Foundation | Thiophene monoamine based organic-inorganic hybrid perovskites |
| CN109880063A (en) * | 2019-02-21 | 2019-06-14 | 深圳大学 | Conjugated polymer and preparation method and application based on benzene thiophene unit |
Non-Patent Citations (3)
| Title |
|---|
| GAJANAN KADAM ET AL.: ""Generating a three-dimensional non-fullerene electron acceptor by combining inexpensive spiro[fluorene-9,9-xanthene] and cyanopyridone functionalities"", 《MATERIALS CHEMISTRY FRONTIERS》 * |
| JOHN R. BERTRAM ET AL.: ""A Novel n-Type Organosilane-Metal Ion Hybrid of Rhodamine B and Copper Cation for Low-Temperature Thermoelectric Materials"", 《APPLIED MATERIALS & INTERFACES》 * |
| 王斌 等: ""有机热电材料研究进展"", 《南昌航空大学学报：自然科学版》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113292529A (en) * | 2021-06-22 | 2021-08-24 | 南京邮电大学 | Method for synthesizing spirofluorene xanthene based on microreactor |
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