CN114230829A - COF film heterojunction with long fluorescence life and preparation method thereof - Google Patents
COF film heterojunction with long fluorescence life and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000013310 covalent-organic framework Substances 0.000 claims abstract description 85
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000243 solution Substances 0.000 claims abstract description 35
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- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 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
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- 238000000034 method Methods 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 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
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- 239000000843 powder Substances 0.000 claims abstract description 13
- 238000009830 intercalation Methods 0.000 claims abstract description 12
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- 239000010408 film Substances 0.000 claims description 17
- 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
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
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- 230000008020 evaporation Effects 0.000 claims description 2
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Abstract
The invention belongs to the field of organic photoelectric materials, and discloses a COF film heterojunction with long fluorescence life and a preparation method thereof. The method comprises the following steps: mixing TFPy-COF, glycerol and ethanol and carrying out 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-tri (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-dihydroxy glyoxal dissolved by hydrochloric acid to obtain TD-COF; and dropping the Py-COF on the TD-COF, and airing to obtain the COF film heterojunction. The COF film heterojunction with the long fluorescence life prepared by the invention has higher fluorescence quantum efficiency and longer fluorescence life.
Description
Technical Field
The invention belongs to the field of organic photoelectric materials, and particularly relates to a COF film heterojunction with long fluorescence life and a preparation method thereof.
Background
A Covalent Organic Framework (COF) is a periodic and crystalline organic porous crystalline material connected by lightweight elements (C, O, N, B, etc.) through Covalent bonds, has the advantages of high specific surface area, low density, easy modification, functionalization, diverse structure, etc., has wide application potential in the aspects of gas adsorption, heterogeneous catalysis, energy storage, photoelectricity, etc., and has attracted strong research interest in the scientific community. However, COFs currently have some defects, for example, COFs generally prepared are powdery, have few active sites and narrow spectral response, which limits the application. COF films tend to expose more active sites, have fewer structural defects, have smooth surfaces, and due to quantum size, the properties of materials at the nanoscale can be greatly different from those of macroscopic bulk and powder materials, for example, the electron transport of the film is faster. A heterojunction refers to an interface region formed by contact coupling of two or more semiconductors. The mode can not only enlarge the visible light absorption range of the material, but also promote the migration of photo-generated charges on different photocatalyst materials and the spatial separation of the photo-generated charges through the close contact between interfaces, so that the structure can be complementary in properties, the advantages of the material are better played, and the excellent improvement of the application performance is realized.
At present, many researchers still study the heterojunction, and the study is still in contact coupling of organic material and inorganic material, however, the inorganic semiconductor has low energy utilization rate, and the application is limited. Therefore, there is a need to provide a COF film heterojunction with long fluorescence lifetime and a method for preparing the same, so as to effectively improve the optical properties and application performance of the polymer.
Disclosure of Invention
The invention aims to provide a COF film heterojunction with long fluorescence lifetime and a preparation method thereof aiming at the defects of the prior art. The COF film heterojunction with the long fluorescence life prepared by the invention has higher fluorescence quantum efficiency and longer fluorescence life.
In order to achieve the above object, the present invention provides, in one aspect, a method for preparing a COF thin film heterojunction having a long fluorescence lifetime, the method comprising the steps of:
s1: preparation of Py-COF: mixing TFPy-COF, glycerol and ethanol and carrying out 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;
s2: preparation of TD-COF: in a reaction vessel, 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-tri (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-dihydroxy glyoxal dissolved by hydrochloric acid to obtain the TD-COF;
s3: preparation of COF thin film heterojunction: and dropping the Py-COF on the TD-COF, and airing to obtain the COF film heterojunction.
According to the invention, the mass ratio of TFPy-COF, glycerol and ethanol is (2.5-3.5) 1: (2.5-3.5).
According to the 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 2.5-3.5 h.
According to the invention, preferably, the calcination treatment is carried out under the protection of nitrogen, the temperature of the calcination treatment is 250-350 ℃, and the time of the calcination treatment is 2.5-3.5 h.
According to the present invention, preferably, the homogeneous mixing of the solid powder with DMF is performed under ultrasonic conditions; the ratio of the solid powder to DMF was 1: (8-12) g/L.
According to the invention, the TFPy-COF is preferably obtained by taking 1,3,6, 8-tetra (4-formaldehyde phenyl) pyrene and p-phenylenediamine as construction plates and mixing the construction plates with a third mixed solution.
According to the invention, the reaction conditions for preparing the TFPy-COF preferably comprise: the reaction temperature is 110 ℃ and 130 ℃, and the reaction time is 70-80 h.
According to the present invention, it is preferable that the ratio of the amounts of the substances of 1,3,6, 8-tetrakis (4-formaldehyde-phenyl) 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: and mixing the o-dichlorobenzene, the n-butanol and the acetic acid solution to obtain the third mixed solution.
According to the invention, the molar concentration of the acetic acid solution is preferably 2.5-3.5 mol/L.
According to the invention, the volume ratio of the o-dichlorobenzene, the n-butanol and the 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 to 2.5 g/L; the volume ratio of the using amount of the chloroform solution dissolved with the sodium dodecyl benzene sulfonate to the using amount of the water is 1: (2200-2500).
According to the present invention, preferably, the hydrochloric acid-dissolved 1,3, 5-tris (4-aminophenyl) benzene has a concentration of 0.5 to 1.5mg/L of 1,3, 5-tris (4-aminophenyl) benzene and a concentration of 0.11 to 0.13mol/L of hydrochloric acid; the volume ratio of the dosage of the 1,3, 5-tri (4-aminophenyl) benzene dissolved by the hydrochloric acid to the dosage of the chloroform solution dissolved with the sodium dodecyl benzene sulfonate is (17-30): 1.
according to the present invention, it is preferable that the concentration of 2, 5-dihydroxyglyoxal in the hydrochloric acid-dissolved 2, 5-dihydroxyglyoxal is 0.5-1.5mg/L, and the concentration of hydrochloric acid is 0.11-0.13 mol/L; the volume ratio of the using amount of the 2, 5-dihydroxy glyoxal dissolved by the hydrochloric acid to the using amount of the chloroform solution dissolved with the sodium dodecyl benzene sulfonate is (12-14): 1.
according to the invention, preferably, the catalyst is acetic acid, the concentration of the acetic acid is 0.015-0.025mol/L, and the volume ratio of the using amount of the acetic acid to the using amount of the chloroform solution dissolved with the sodium dodecyl benzene sulfonate is (190-210): 1.
according to the invention, the time of the evaporation treatment is preferably 15-25 min.
According to the present invention, it is preferable that the reaction time of the first solution with 1,3, 5-tris (4-aminophenyl) benzene dissolved by hydrochloric acid is 0.8 to 1.2 hours.
According to the present invention, it is preferable that the reaction time of the second mixed solution with the catalyst and the 2, 5-dihydroxyglyoxal dissolved by hydrochloric acid is 4.5 to 5.5 d.
According to the present invention, preferably, said step S2 is performed at 20-30 ℃.
The invention also provides the COF film heterojunction with the long fluorescence life prepared by the preparation method of the COF film heterojunction with the long fluorescence life.
The technical scheme of the invention has the following beneficial effects:
(1) step S1 of the method is realized by a glycerin intercalation method; step S2 is realized by a surfactant-single film auxiliary interface synthesis method; step S3 is to form an effective heterojunction structure by using van der waals force between the thin films.
(2) The method solves the problem of limited application of COF due to 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 the process, high purity of the obtained product and cost saving.
(3) The COF film heterojunction with the long fluorescence life has the advantages of high fluorescence quantum efficiency, long fluorescence life and wide application prospect, and can be used for preparing organic porous materials with controllable structures, wide photoresponse range and adjustable energy band structures.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent by describing in more detail exemplary embodiments thereof with reference to the attached drawings, in which like reference numerals generally represent like parts throughout.
FIG. 1 shows a spectrum of fluorescence lifetime curve of a COF thin film heterojunction Py-COF/TD-COF prepared in example 1 of the present invention (wherein Intensity is Intensity; Time is Time).
FIG. 2 shows Fluorescence emission spectra of a COF thin film heterojunction Py-COF/TD-COF and a Py-COF prepared in different dosage ratios of Py-COF and TD-COF in example 1 of the present invention and Fluorescence emission spectra of the Py-COF and the TD-COF (wherein: Fluorescence Intensity and Wavelength are shown).
FIG. 3 shows a peel off metallographic micrograph of Py-COF of inventive example 1.
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 following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by 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 film heterojunction with long fluorescence lifetime, which comprises the following steps:
s1: preparation of Py-COF: mixing TFPy-COF, glycerol and ethanol and carrying out intercalation reaction in a flask to obtain a reaction product; washing, centrifuging, drying and calcining the reaction product in sequence to obtain solid powder; uniformly mixing 1mg of the solid powder with 10mL of DMF under an ultrasonic condition to obtain the Py-COF;
wherein: the mass ratio of the TFPy-COF to the glycerol to the 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 h.
The TFPy-COF is prepared by taking 1,3,6, 8-tetra (4-formaldehyde phenyl) pyrene (20mg) and p-phenylenediamine (7mg) as basic building blocks and reacting for 72 hours at 120 ℃ under the conditions 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 dish, and evaporating the chloroform in the solution for 20min to obtain a first solution; mixing the first solution with 355 mu L of 1,3, 5-tri (4-aminophenyl) benzene dissolved by hydrochloric acid and reacting for 1h to obtain a second mixed solution; mixing the second mixed solution with 4mL of catalyst and 250 mu L of 2, 5-dihydroxy glyoxal dissolved by hydrochloric acid and reacting for 5d to obtain the TD-COF;
wherein: the concentration of the sodium dodecyl benzene sulfonate in the chloroform solution dissolved with the sodium dodecyl benzene sulfonate is 2 g/L;
the concentration of 1,3, 5-tri (4-aminophenyl) benzene in the 1,3, 5-tri (4-aminophenyl) benzene dissolved by the hydrochloric acid is 1mg/L, and the concentration of the hydrochloric acid is 0.12 mol/L;
the concentration of the 2, 5-dihydroxy glyoxal in the 2, 5-dihydroxy glyoxal dissolved by the hydrochloric acid is 1mg/L, and the concentration of the hydrochloric acid is 0.12 mol/L;
the catalyst is acetic acid, and the concentration of the acetic acid is 0.02 mol/L;
said step S2 is carried out at 25 ℃.
S3: preparation of COF thin film heterojunction: and dropping the Py-COF on the TD-COF, and airing to obtain the COF film heterojunction Py-COF/TD-COF.
Wherein the amounts of Py-COF are 0.5 parts, 5 parts and 10 parts, respectively, based on 100 parts by weight of TD-COF, and the fluorescence emission spectra of Py-COF and TD-COF are shown in FIG. 2.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not 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 described embodiments.
Claims (10)
1. A preparation method of a COF film heterojunction with long fluorescence lifetime is characterized by comprising the following steps:
s1: preparation of Py-COF: mixing TFPy-COF, glycerol and ethanol and carrying out 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;
s2: preparation of TD-COF: in a reaction vessel, 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-tri (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-dihydroxy glyoxal dissolved by hydrochloric acid to obtain the TD-COF;
s3: preparation of COF thin film heterojunction: and dropping the Py-COF on the TD-COF, and airing to obtain the COF film heterojunction.
2. The method for preparing COF thin film heterojunction with long fluorescence lifetime as claimed in claim 1, wherein the mass ratio of TFPy-COF, glycerol and ethanol is (2.5-3.5) 1: (2.5-3.5).
3. The preparation method of COF thin film heterojunction with long fluorescence lifetime as claimed in 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 2.5-3.5 h.
4. The method for preparing the COF thin film heterojunction with long fluorescence lifetime as claimed in 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 2.5-3.5 h.
5. The method for preparing a COF thin film heterojunction with long fluorescence lifetime as claimed in claim 1, wherein the uniform mixing of the solid powder and DMF is performed under ultrasonic conditions; the ratio of the solid powder to DMF was 1: (8-12) g/L.
6. The method for preparing the COF thin film heterojunction with long fluorescence lifetime as claimed in claim 1, wherein the TFPy-COF is prepared by mixing 1,3,6, 8-tetra (4-formaldehyde phenyl) pyrene and p-phenylenediamine as a building block with a third mixed solution;
the reaction conditions for preparing the TFPy-COF include: the reaction temperature is 110-;
the mass ratio of the 1,3,6, 8-tetra (4-formaldehyde phenyl) pyrene to the p-phenylenediamine is 1: (1.9-2.1);
the preparation method of the third mixed solution comprises the following steps: and mixing the o-dichlorobenzene, the n-butanol and the acetic acid solution to obtain the third mixed solution.
7. The method for preparing COF thin film heterojunction with long fluorescence lifetime as claimed in claim 6, wherein,
the molar concentration of the acetic acid solution is 2.5-3.5 mol/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 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 1.5-2.5 g/L; the volume ratio of the using amount of the chloroform solution dissolved with the sodium dodecyl benzene sulfonate to the using amount of the water is 1: (2200-;
the concentration of 1,3, 5-tri (4-aminophenyl) benzene in the 1,3, 5-tri (4-aminophenyl) benzene dissolved by the hydrochloric acid is 0.5-1.5mg/L, and the concentration of the hydrochloric acid is 0.11-0.13 mol/L; the volume ratio of the dosage of the 1,3, 5-tri (4-aminophenyl) benzene dissolved by the hydrochloric acid to the dosage of the chloroform solution dissolved with the sodium dodecyl benzene sulfonate is (17-30): 1;
the concentration of the 2, 5-dihydroxy glyoxal in the 2, 5-dihydroxy glyoxal dissolved by the hydrochloric acid is 0.5-1.5mg/L, and the concentration of the hydrochloric acid is 0.11-0.13 mol/L; the volume ratio of the using amount of the 2, 5-dihydroxy glyoxal dissolved by the hydrochloric acid to the using amount of the chloroform solution dissolved with the sodium dodecyl benzene sulfonate is (12-14): 1;
the catalyst is acetic acid, the concentration of the acetic acid is 0.015-0.025mol/L, and the volume ratio of the dosage of the acetic acid to the dosage of the chloroform solution dissolved with the sodium dodecyl benzene sulfonate is (190-210): 1.
9. the method for preparing COF thin film heterojunction with long fluorescence lifetime as claimed in claim 1, wherein,
the time of the evaporation treatment is 15-25 min;
the reaction time of the first solution and 1,3, 5-tri (4-aminophenyl) benzene dissolved by hydrochloric acid is 0.8-1.2 h;
the reaction time of the second mixed solution, the catalyst and the 2, 5-dihydroxy glyoxal dissolved by hydrochloric acid is 4.5-5.5 days;
the step S2 is carried out at 20-30 ℃.
10. The COF thin film heterojunction with long fluorescence lifetime prepared by the method for preparing the COF thin film heterojunction with long fluorescence lifetime according to any one of claims 1 to 9.
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