CN114230829B - COF (chip on film) thin film heterojunction with long fluorescence lifetime and preparation method thereof - Google Patents
COF (chip on film) thin film heterojunction with long fluorescence lifetime and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000010408 film Substances 0.000 title abstract description 14
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 52
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 38
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 21
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
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- 238000000034 method Methods 0.000 claims abstract description 15
- QHQSCKLPDVSEBJ-UHFFFAOYSA-N 1,3,5-tri(4-aminophenyl)benzene Chemical compound C1=CC(N)=CC=C1C1=CC(C=2C=CC(N)=CC=2)=CC(C=2C=CC(N)=CC=2)=C1 QHQSCKLPDVSEBJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 14
- 238000009830 intercalation Methods 0.000 claims abstract description 12
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- 238000001704 evaporation Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 42
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- 235000011187 glycerol Nutrition 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims description 6
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 3
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- XDIQTPZOIIYCTR-GRFIIANRSA-N [[(2r,3s,4r,5r)-5-(6-aminopurin-9-yl)-4-hydroxy-3-phosphonooxyoxolan-2-yl]methoxy-hydroxyphosphoryl] [(3r)-3-hydroxy-2,2-dimethyl-4-oxo-4-[[3-oxo-3-[2-(3,3,3-trifluoro-2-oxopropyl)sulfanylethylamino]propyl]amino]butyl] hydrogen phosphate Chemical compound O[C@@H]1[C@H](OP(O)(O)=O)[C@@H](COP(O)(=O)OP(O)(=O)OCC(C)(C)[C@@H](O)C(=O)NCCC(=O)NCCSCC(=O)C(F)(F)F)O[C@H]1N1C2=NC=NC(N)=C2N=C1 XDIQTPZOIIYCTR-GRFIIANRSA-N 0.000 claims 13
- 239000000463 material Substances 0.000 abstract description 6
- 239000004065 semiconductor Substances 0.000 description 3
- ZGLHKEJAGHMUHR-UHFFFAOYSA-N 4-[3,6,8-tris(4-formylphenyl)pyren-1-yl]benzaldehyde Chemical compound C1=CC(C=O)=CC=C1C(C1=CC=C23)=CC(C=4C=CC(C=O)=CC=4)=C(C=C4)C1=C2C4=C(C=1C=CC(C=O)=CC=1)C=C3C1=CC=C(C=O)C=C1 ZGLHKEJAGHMUHR-UHFFFAOYSA-N 0.000 description 2
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- 229910021641 deionized water Inorganic materials 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
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Abstract
The invention belongs to the field of organic photoelectric materials, and discloses a COF (chip on film) thin film heterojunction with long fluorescence lifetime and a preparation method thereof. The method comprises the following steps: mixing TFPy-COF, glycerol and ethanol, and performing intercalation reaction to obtain a reaction product; washing, centrifuging, drying and calcining the reaction product in sequence to obtain solid powder; uniformly mixing the solid powder with DMF to obtain Py-COF; dispersing a chloroform solution dissolved with sodium dodecyl benzene sulfonate on a water interface, and evaporating chloroform in the solution to obtain a first solution; mixing and reacting the first solution with 1,3, 5-tris (4-aminophenyl) benzene dissolved by hydrochloric acid to obtain a second mixed solution; mixing and reacting the second mixed solution with a catalyst and 2, 5-dihydroxyglyoxal dissolved by hydrochloric acid to obtain TD-COF; and (3) dripping the Py-COF on the TD-COF, and airing to obtain the COF thin film heterojunction. The COF film heterojunction with long fluorescence lifetime prepared by the invention has higher fluorescence quantum efficiency and longer fluorescence lifetime.
Description
Technical Field
The invention belongs to the field of organic photoelectric materials, and particularly relates to a COF (chip on film) thin film heterojunction with long fluorescence lifetime and a preparation method thereof.
Background
The covalent organic frameworks (Covalent organic frameworks, COF) are organic porous crystalline materials with periodicity and crystallinity, which are connected by light elements (C, O, N, B, etc.) through covalent bonds, have the advantages of high specific surface area, low density, easy modification, functionalization, multiple structures, and the like, have wide application potential in the aspects of gas adsorption, heterogeneous catalysis, energy storage, photoelectricity, and the like, and are of great research interest in the scientific community. However, COFs have some drawbacks, such as powder form, few active sites and narrow spectral response, which limit their application. COF films tend to expose more active sites, have fewer structural defects, have smooth surfaces, and due to quantum size effects, the nanoscale material may differ significantly from macroscopic bulk, powder material properties, e.g., film electron transport is faster. Heterojunction refers to an interface region formed by the contact coupling of two or more semiconductors. The mode can expand the visible light absorption range of the material, promote the migration of photo-generated charges on different photocatalyst materials through the tight contact between interfaces, promote the spatial separation of the photo-generated charges, make the structure have complementary properties, better exert the advantages of the material and realize the excellent improvement of application performance.
At present, many researchers' researches on heterojunction still stay in contact coupling of organic materials and inorganic materials, however, inorganic semiconductors have low energy utilization rate, and limit the application of the inorganic semiconductors. Therefore, it is needed to propose a COF thin film heterojunction with long fluorescence lifetime and a preparation method thereof, so as to effectively improve the optical properties and application performance of the polymer.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art and provides a COF thin film heterojunction with long fluorescence lifetime and a preparation method thereof. The COF film heterojunction with long fluorescence lifetime prepared by the invention has higher fluorescence quantum efficiency and longer fluorescence lifetime.
In order to achieve the above object, the present invention provides a method for preparing a COF thin film heterojunction with long fluorescence lifetime, comprising the steps of:
S1: preparation of Py-COF: mixing TFPy-COF, glycerol and ethanol, and performing intercalation reaction to obtain a reaction product; washing, centrifuging, drying and calcining the reaction product in sequence to obtain solid powder; uniformly mixing the solid powder with DMF to obtain the Py-COF;
S2: preparation of TD-COF: dispersing a chloroform solution dissolved with sodium dodecyl benzene sulfonate on a water interface in a reaction container, and evaporating chloroform in the solution to obtain a first solution; mixing and reacting the first solution with 1,3, 5-tris (4-aminophenyl) benzene dissolved by hydrochloric acid to obtain a second mixed solution; mixing and reacting the second mixed solution with a catalyst and 2, 5-dihydroxyglyoxal dissolved by hydrochloric acid to obtain the TD-COF;
S3: preparation of COF thin film heterojunction: and (3) dripping the Py-COF on the TD-COF, and airing to obtain the COF thin film heterojunction.
According to the present invention, preferably, the mass ratio of TFPy-COF, glycerin and ethanol is (2.5-3.5): 1: (2.5-3.5).
According to the present invention, preferably, the intercalation reaction is carried out under ultrasonic conditions, the temperature of the intercalation reaction is 85-95 ℃, and the time of the intercalation reaction is 2.5-3.5h.
According to the present invention, preferably, the calcination treatment is performed under nitrogen protection, the temperature of the calcination treatment is 250-350 ℃, and the time of the calcination treatment is 2.5-3.5 hours.
According to the present invention, preferably, the uniform mixing of the solid powder with DMF is performed under ultrasonic conditions; the ratio of solid powder to DMF was 1: (8-12) g/L.
According to the present invention, preferably, the TFPy-COF is obtained by using 1,3,6, 8-tetrakis (4-formylphenyl) pyrene and p-phenylenediamine as building blocks and mixing with the third mixed solution.
According to the present invention, preferably, the reaction conditions for preparing the TFPy-COF include: the reaction temperature is 110-130 ℃ and the reaction time is 70-80h.
According to the present invention, preferably, the ratio of the amounts of the substances of 1,3,6, 8-tetrakis (4-formylphenyl) pyrene and p-phenylenediamine is 1: (1.9-2.1).
According to the present invention, preferably, the preparation method of the third mixed solution includes: mixing o-dichlorobenzene, n-butanol and acetic acid solution to obtain the third mixed solution.
According to the present invention, preferably, the molar concentration of the acetic acid solution is 2.5 to 3.5mol/L.
According to the present invention, preferably, the volume ratio of the o-dichlorobenzene, n-butanol and acetic acid solution is (4.5-5.5): (4.5-5.5): 1.
According to the present invention, preferably, the concentration of sodium dodecylbenzenesulfonate in the chloroform solution in which sodium dodecylbenzenesulfonate is dissolved is 1.5-2.5g/L; the volume ratio of the dosage of the chloroform solution dissolved with the sodium dodecyl benzene sulfonate to the dosage of water is 1: (2200-2500).
According to the present invention, preferably, the concentration of 1,3, 5-tris (4-aminophenyl) benzene in the hydrochloric acid-dissolved 1,3, 5-tris (4-aminophenyl) benzene is 0.5 to 1.5mg/L, and the concentration of hydrochloric acid is 0.11 to 0.13mol/L; the volume ratio of the amount of the 1,3, 5-tris (4-aminophenyl) benzene dissolved in the hydrochloric acid to the amount of the chloroform solution dissolved with sodium dodecylbenzenesulfonate is (17-30): 1.
According to the present invention, preferably, the concentration of 2, 5-dihydroxyglyoxal in the hydrochloric acid-dissolved 2, 5-dihydroxyglyoxal is 0.5 to 1.5mg/L, and the concentration of hydrochloric acid is 0.11 to 0.13mol/L; the volume ratio of the amount of the 2, 5-dihydroxyglyoxal dissolved by the hydrochloric acid to the amount of the chloroform solution dissolved with the sodium dodecyl benzene sulfonate is (12-14): 1.
According to the present invention, preferably, the catalyst is acetic acid, the concentration of the acetic acid is 0.015 to 0.025mol/L, and the volume ratio of the amount of the acetic acid to the amount of the chloroform solution in which sodium dodecylbenzenesulfonate is dissolved is (190 to 210): 1.
According to the present invention, preferably, the time of the evaporation treatment is 15 to 25 minutes.
According to the present invention, it is preferable that the first solution is reacted with 1,3, 5-tris (4-aminophenyl) benzene dissolved by hydrochloric acid for 0.8 to 1.2 hours.
According to the present invention, preferably, the second mixed solution is reacted with the catalyst and 2, 5-dihydroxyglyoxal dissolved by hydrochloric acid for a time of 4.5 to 5.5d.
According to the invention, preferably, said step S2 is carried out at 20-30 ℃.
The invention also provides the COF film heterojunction with long fluorescence lifetime prepared by the preparation method of the COF film heterojunction with long fluorescence lifetime.
The technical scheme of the invention has the following beneficial effects:
(1) Step S1 of the method is realized by a glycerol intercalation method; step S2 is realized by a surfactant-single membrane auxiliary interface synthesis method; step S3 is to form an effective heterojunction structure using van der waals forces between the films.
(2) The invention solves the problem of limited application of COF caused by low quantum efficiency, low carrier mobility, easy recombination of electron holes and the like, and has the advantages of simple required equipment, easy control of technological process, high purity of the obtained product and cost saving.
(3) The COF film heterojunction with long fluorescence lifetime prepared by the method has higher fluorescence quantum efficiency, longer fluorescence lifetime and wider application prospect, and can be used for preparing organic porous materials with controllable structure, wide light response range and adjustable energy band structure.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The foregoing and other objects, features and advantages of the invention will be apparent from the following more particular descriptions of exemplary embodiments of the invention as illustrated in the accompanying drawings wherein like reference numbers generally represent like parts throughout the exemplary embodiments of the invention.
FIG. 1 shows a graph of fluorescence lifetime curves (wherein: intensity; time) of the COF thin film heterojunction Py-COF/TD-COF prepared in example 1 of the present invention.
FIG. 2 shows the fluorescence emission spectra of Py-COF/TD-COF and Py-COF and TD-COF of the COF film heterojunction prepared in example 1 of the present invention under different dosage ratios (wherein Fluorescence Intensity is fluorescence intensity; wavelength is wavelength).
FIG. 3 shows a peel metallographic micrograph of Py-COF of example 1 of the present invention.
Fig. 4 shows a metallographic microscopic image of the TD-COF film of example 1 of the present invention.
Fig. 5 shows a metallographic microscopic image of the COF thin film heterojunction Py-COF/TD-COF of example 1 of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention are described below, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
Example 1
The embodiment provides a preparation method of a COF thin film heterojunction with long fluorescence lifetime, which comprises the following steps:
S1: preparation of Py-COF: TFPy-COF, glycerol and ethanol are mixed and are subjected to intercalation reaction in a flask, so that a reaction product is obtained; washing, centrifuging, drying and calcining the reaction product in sequence to obtain solid powder; taking 1mg of the solid powder and 10mL of DMF, and uniformly mixing under ultrasonic conditions to obtain the Py-COF;
wherein: the mass ratio of TFPy-COF, glycerol and ethanol is 3:1:3;
The intercalation reaction is carried out under the ultrasonic condition, the temperature is 90 ℃, and the time is 3 hours;
The calcination treatment is carried out under the protection of nitrogen, the temperature is 300 ℃, and the time is 3 hours.
The TFPy-COF is prepared by taking 1,3,6, 8-tetra (4-formaldehyde phenyl) pyrene (20 mg) and p-phenylenediamine (7 mg) as basic building blocks and reacting for 72 hours at 120 ℃ under the condition of o-dichlorobenzene/n-butanol/3M acetic acid (5:5:1).
S2: preparation of TD-COF: dispersing 2 mu L of chloroform solution dissolved with sodium dodecyl benzene sulfonate on a 45mL deionized water interface in a crystallization vessel, and evaporating chloroform in the solution for 20min to obtain a first solution; mixing and reacting 355 μl of 1,3, 5-tris (4-aminophenyl) benzene dissolved by hydrochloric acid for 1h to obtain a second mixed solution; mixing and reacting the second mixed solution with 4mL of catalyst and 250 mu L of 2, 5-dihydroxyglyoxal dissolved by hydrochloric acid for 5d to obtain the TD-COF;
wherein: the concentration of sodium dodecyl benzene sulfonate in the chloroform solution dissolved with sodium dodecyl benzene sulfonate is 2g/L;
the concentration of 1,3, 5-tri (4-aminophenyl) benzene in the 1,3, 5-tri (4-aminophenyl) benzene dissolved by hydrochloric acid is 1mg/L, and the concentration of hydrochloric acid is 0.12mol/L;
The concentration of 2, 5-dihydroxyglyoxal in the 2, 5-dihydroxyglyoxal dissolved by hydrochloric acid is 1mg/L, and the concentration of hydrochloric acid is 0.12mol/L;
the catalyst is acetic acid, and the concentration of the acetic acid is 0.02mol/L;
the step S2 is carried out at 25 ℃.
S3: preparation of COF thin film heterojunction: and (3) dripping the Py-COF on the TD-COF, and airing to obtain the COF thin film heterojunction Py-COF/TD-COF.
Wherein, the dosages of Py-COF are respectively 0.5 part, 5 parts and 10 parts by weight based on 100 parts by weight of the TD-COF, and the fluorescence emission spectra of Py-COF and TD-COF with different dosage ratios are shown in figure 2.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.
Claims (10)
1. A method for preparing a COF thin film heterojunction with long fluorescence lifetime, which is characterized by comprising the following steps:
S1: preparation of Py-COF: mixing TFPy-COF, glycerol and ethanol, and performing intercalation reaction to obtain a reaction product; washing, centrifuging, drying and calcining the reaction product in sequence to obtain solid powder; uniformly mixing the solid powder with DMF to obtain the Py-COF;
The TFPy-COF is prepared by taking 1,3,6, 8-tetra (4-formaldehyde phenyl) pyrene and p-phenylenediamine as building blocks and mixing with a third mixed solution;
S2: preparation of TD-COF: dispersing a chloroform solution dissolved with sodium dodecyl benzene sulfonate on a water interface in a reaction container, and evaporating chloroform in the solution to obtain a first solution; mixing and reacting the first solution with 1,3, 5-tris (4-aminophenyl) benzene dissolved by hydrochloric acid to obtain a second mixed solution; mixing and reacting the second mixed solution with a catalyst and 2, 5-dihydroxyglyoxal dissolved by hydrochloric acid to obtain the TD-COF;
S3: preparation of COF thin film heterojunction: and (3) dripping the Py-COF on the TD-COF, and airing to obtain the COF thin film heterojunction.
2. The method for preparing a COF thin film heterojunction with long fluorescence lifetime as claimed in claim 1, wherein the mass ratio of TFPy-COF, glycerin and ethanol is (2.5-3.5): 1: (2.5-3.5).
3. The method for preparing a COF thin film heterojunction with long fluorescence lifetime of claim 1, wherein the intercalation reaction is carried out under ultrasonic conditions, the temperature of the intercalation reaction is 85-95 ℃, and the time of the intercalation reaction is 2.5-3.5h.
4. The method for preparing a COF thin film heterojunction with long fluorescence lifetime of claim 1, wherein the calcination treatment is performed under the protection of nitrogen, the temperature of the calcination treatment is 250-350 ℃, and the time of the calcination treatment is 2.5-3.5h.
5. The method for preparing a COF thin film heterojunction with long fluorescence lifetime according to claim 1, wherein the uniform mixing of the solid powder and DMF is performed under ultrasonic conditions; the ratio of solid powder to DMF was 1: (8-12) g/L.
6. The method for preparing a COF thin film heterojunction with long fluorescence lifetime as claimed in claim 1, wherein,
The reaction conditions for preparing the TFPy-COF include: the reaction temperature is 110-130 ℃ and the reaction time is 70-80h;
the ratio of the amounts of the substances of the 1,3,6, 8-tetra (4-formaldehyde phenyl) pyrene and the p-phenylenediamine is 1: (1.9-2.1);
the preparation method of the third mixed solution comprises the following steps: mixing o-dichlorobenzene, n-butanol and acetic acid solution to obtain the third mixed solution.
7. The method for preparing a COF thin film heterojunction with long fluorescence lifetime as claimed in claim 6, wherein,
The molar concentration of the acetic acid solution is 2.5-3.5mol/L;
The volume ratio of the o-dichlorobenzene to the n-butanol to the acetic acid solution is (4.5-5.5): (4.5-5.5): 1.
8. The method for preparing a COF thin film heterojunction with long fluorescence lifetime as claimed in claim 1, wherein,
The concentration of the sodium dodecyl benzene sulfonate in the chloroform solution dissolved with the sodium dodecyl benzene sulfonate is 1.5-2.5g/L; the volume ratio of the dosage of the chloroform solution dissolved with the sodium dodecyl benzene sulfonate to the dosage of water is 1: (2200-2500);
The concentration of the 1,3, 5-tri (4-aminophenyl) benzene in the 1,3, 5-tri (4-aminophenyl) benzene dissolved by hydrochloric acid is 0.5-1.5mg/L, and the concentration of the hydrochloric acid is 0.11-0.13mol/L; the volume ratio of the amount of the 1,3, 5-tris (4-aminophenyl) benzene dissolved in the hydrochloric acid to the amount of the chloroform solution dissolved with sodium dodecylbenzenesulfonate is (17-30): 1, a step of;
The concentration of 2, 5-dihydroxyglyoxal in the 2, 5-dihydroxyglyoxal dissolved by hydrochloric acid is 0.5-1.5mg/L, and the concentration of hydrochloric acid is 0.11-0.13mol/L; the volume ratio of the amount of the 2, 5-dihydroxyglyoxal dissolved by the hydrochloric acid to the amount of the chloroform solution dissolved with the sodium dodecyl benzene sulfonate is (12-14): 1, a step of;
The catalyst is acetic acid, the concentration of the acetic acid is 0.015-0.025mol/L, and the volume ratio of the amount of the acetic acid to the amount of the chloroform solution dissolved with sodium dodecyl benzene sulfonate is (190-210): 1.
9. The method for preparing a COF thin film heterojunction with long fluorescence lifetime as claimed in claim 1, wherein,
The evaporation treatment time is 15-25min;
The reaction time of the first solution and 1,3, 5-tris (4-aminophenyl) benzene dissolved by hydrochloric acid is 0.8 to 1.2 hours;
the reaction time of the second mixed solution with the catalyst and the 2, 5-dihydroxyglyoxal dissolved by hydrochloric acid is 4.5-5.5d;
the step S2 is carried out at 20-30 ℃.
10. COF thin film heterojunction with long fluorescence lifetime prepared by the preparation method of COF thin film heterojunction with long fluorescence lifetime according to any one of claims 1 to 9.
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