CN117181303A - Three-dimensional covalent organic framework@metal halide perovskite composite material and preparation method and application thereof - Google Patents
Three-dimensional covalent organic framework@metal halide perovskite composite material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 35
- 229910001507 metal halide Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000013476 3D covalent-organic framework Substances 0.000 claims abstract description 76
- 239000000463 material Substances 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 30
- YXCKIFUUJXNFIW-UHFFFAOYSA-N 5-[4-(1,3-dioxo-2-benzofuran-5-yl)phenyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C2=CC=C(C=C2)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 YXCKIFUUJXNFIW-UHFFFAOYSA-N 0.000 claims abstract description 15
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- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011941 photocatalyst Substances 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 42
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 31
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical group ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
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- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 3
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Abstract
The invention relates to a three-dimensional covalent organic framework@metal halide perovskite composite material and a preparation method and application thereof, wherein the method comprises the following steps of adding BTD and Por-8NH in a first solvent 2 Reacting with TPDA, and after the reaction is finished, performing post-treatment to obtain the 3D COF material; in a second solvent, reacting the 3D COF material with lead halide, and performing post-treatment after the reaction is finished to obtain the 3D COF@PbX 2 A material; in a third solvent, 3D COF@PbX 2 Reacting the material with methyl iodide, and post-treating after the reaction to obtain 3D COF@MAPbX 3 A composite material. The 3D COF@MAPbX of the invention 3 The composite material can be used as a photocatalyst, and has the advantage of good photocatalytic activity; in addition, the preparation method enables perovskite quantum dots to grow in situ in the pore canal of the COF, and is used for solving the problems of poor stability, insufficient photocatalytic activity and the like of the perovskite quantum dots in the environment.
Description
Technical Field
The invention relates to the technical field of organic-inorganic composite materials, in particular to a three-dimensional covalent organic framework@metal halide perovskite composite material, and a preparation method and application thereof.
Background
Photocatalytic reduction of carbon dioxide to value-added chemical fuels is an effective method to address energy crisis and global warming. MAPbX 3 (x=br, I) quantum dots become CO due to their excellent optoelectronic properties including high molar extinction coefficient, low exciton binding energy and defect tolerance 2 Good candidates for reduction. However, the original MAPbX 3 (x=br, I) quantum dots generally have lower photocatalytic performance, mainly due to the predominance of charge recombination and lack of efficient CO 2 Adsorption/activation of catalytic sites.
Covalent Organic Frameworks (COFs) are novel crystalline porous organic polymers with unique properties of photocatalytic CO 2 Reduction provides an ideal levelA stage: 1) Good chemical and thermodynamic stability ensures robustness in its catalytic process; 2) The structure is easy to modify and functionalize, which is favorable for loading various active sites and is convenient for synthesizing functional materials based on COFs; 3) COFs with high porosity and large surface area can ensure CO 2 Adsorption and rapid mass transfer; 4) The chemical composition and structure of known COFs can provide an accurate structural model to facilitate resolution of the reaction mechanism. However, COFs materials constructed from organic materials always lack effective active sites, resulting in difficulty in achieving excellent performance as photocatalysts. Therefore, it is particularly critical to develop a photocatalyst that is efficient and stable.
Disclosure of Invention
Aiming at the defects existing in the prior art, the first aim of the invention is to provide a preparation method of a three-dimensional covalent organic framework@metal halide perovskite composite material, so that perovskite quantum dots grow in situ in a pore channel of a COF, and the problems of poor stability, insufficient photocatalytic activity and the like of the perovskite quantum dots in the environment are solved.
The second object of the invention is to provide a three-dimensional covalent organic framework@metal halide perovskite composite material which has the advantage of good photocatalytic activity.
A third object of the present invention is to provide the use of a three-dimensional covalent organic framework @ metal halide perovskite composite material which can be used as a photocatalyst.
In order to achieve the first object, the present invention provides the following technical solutions:
a preparation method of a three-dimensional covalent organic framework@metal halide perovskite composite material comprises the following steps,
s1 in a first solvent, BTD and Por-8NH are added 2 Reacting with TPDA, and after the reaction is finished, performing post-treatment to obtain the 3D COF material;
s2, in a second solvent, carrying out the 3D COF material obtained in the S1 and lead halideReacting, and after the reaction is finished, performing post-treatment to obtain the 3D COF@PbX 2 A material;
s3 in a third solvent, the 3D COF@PbX obtained by the S2 is prepared 2 Reacting the material with methyl iodide, and post-treating after the reaction to obtain 3D COF@MAPbX 3 A composite material.
Further, in the step S1, the first solvent is o-dichlorobenzene, n-butanol and 8-10M acetic acid.
Further, in the S1, BTD, por-8NH is controlled 2 The mass volume ratio of TPDA, o-dichlorobenzene, n-butyl alcohol and acetic acid is 5-20 mg: 10-30 mg: 5-15 mg: 200-1000 [ mu ] L: 200-1000 [ mu ] L: 0-200 mu L.
In the S1, BTD and Por-8NH are firstly added 2 And TPDA is put into a vacuum tube, o-dichlorobenzene and n-butanol are put into the vacuum tube, ultrasonic dispersion is carried out uniformly, acetic acid is put into the vacuum tube, the vacuum tube is frozen and thawed and degassed for 2 to 4 times in 77K liquid nitrogen, the vacuum tube is sealed and reacts for 2 to 7 days at the temperature of 100 to 150 ℃, after the reaction is finished, the reactant is washed by DMF and/or acetone, the washing solid and the acetone are extracted for 1 to 3 days, and then the vacuum drying is carried out for 4 to 10 hours at the temperature of 50 to 120 ℃ to obtain the 3D COF material.
Further, in the step S2, the second solvent is N, N-dimethylformamide and ethanol, and the lead halide is one or a combination of a plurality of lead chloride, lead bromide and lead iodide.
Further, in the step S2, the volume ratio of N, N-dimethylformamide to ethanol is controlled to be 1: 8-10, immersing the 3D COF material in the second solution, and enabling the concentration of the lead halide in the second solution to be 0.8-1.2 mM.
In the S2, the 3D COF material obtained in the S1 is immersed into PbX 2 And a second solvent, soaking the mixture for 0.5 to 1.5 hours to ensure PbX 2 Fully entering a pore canal of a 3D COF material, centrifuging the reaction liquid after the reaction is finished, washing the solid obtained by centrifugation with pure ethanol for 2-4 times to obtain the 3D COF@PbX 2 A material.
Further, in the step S3, the third solvent is ethanol, and the solubility of the methyl iodide in the third solvent is 0.8 to 1.2mm.
Further, in S3, 3D COF@PbX obtained in S2 is used 2 Immersing the material into a solution of methyl iodide and a third solvent, carrying out an immersion reaction for 5-15 min, washing 2-4 times with pure ethanol after the reaction is finished, and carrying out vacuum drying for 4-10 h at 40-60 ℃ to obtain the 3D COF@MAPbX 3 A composite material.
In order to achieve the second object, the present invention provides the following technical solutions:
the three-dimensional covalent organic framework@metal halide perovskite composite material is prepared by adopting the preparation method.
In order to achieve the third object, the present invention provides the following technical solutions:
the three-dimensional covalent organic framework@metal halide perovskite composite material is prepared by the preparation method.
In summary, the beneficial technical effects of the invention are as follows:
1. compared with a 2D COF, the 3D COF prepared by the design of the invention has higher specific surface area, a penetrating pore canal and an open active site, and the pore size of the COF is suitable for MAPbX 3 QDs (x=cl, br, I) grow in situ.
2. The invention provides an in-situ growth MAPbX in a COFs pore canal 3 (x=cl, br, I).
3. The synthesis method is simple, easy to operate and can be realized at room temperature.
Drawings
FIG. 1 is a nuclear magnetic resonance image of BTD of example 1 of the present invention.
FIG. 2 is a view of a Por-8NH according to example 1 of the present invention 2 Is a nuclear magnetic resonance image of (a).
Fig. 3 is a flow chart of the preparation of the 3D COF material of example 1 of the present invention.
FIG. 4 is an XRD pattern of the 3D COF material prepared in example 2 of the present invention; wherein the graph is Bragg, differences, simulated, experimental and Pawley defined from bottom to top.
FIG. 5 is a drawing of a sample of the present invention obtained in example 2N of 3D COF material 2 Adsorption and desorption graph.
Fig. 6 is a pore size distribution diagram of a 3D COF material prepared in example 2 of the present invention.
FIG. 7 shows the CO at different temperatures of the 3D COF material prepared in example 2 of the present invention 2 Adsorption and desorption performance diagram.
FIG. 8 shows the 3D COF@MAPbBr prepared in example 8 of the present invention 3 XRD pattern of the composite material.
FIG. 9 shows the 3D COF@MAPbBr prepared in example 8 of the present invention 3 Composite (below) and 3D COF@MAPbI prepared in example 9 3 TEM image of the composite (upper).
FIG. 10 shows a 3D COF material prepared in example 2 of the present invention, and a 3D COF@MAPbBr prepared in example 8 3 Composite material and 3D COF@MAPbI prepared in example 9 3 Ultraviolet absorption spectrum of the composite material.
Detailed Description
The invention will be further described with reference to the drawings and detailed description in order to make the technical means, the creation characteristics, the achievement of the objects and the functions of the invention more clear and easy to understand.
Examples
Example 1: referring to fig. 1-3, the preparation method of the three-dimensional covalent organic framework@metal halide perovskite composite material disclosed by the invention comprises the following steps,
s1 in a first solvent, BTD and Por-8NH are added 2 Reacting with TPDA, and after the reaction is finished, performing post-treatment to obtain the 3D COF material;
s2, in a second solvent, reacting the 3D COF material obtained in the S1 with lead halide, and performing post-treatment after the reaction is finished to obtain the 3D COF@PbX 2 A material;
s3 in a third solvent, 3D COF@PbX obtained by S2 2 Reacting the material with methyl iodide, and post-treating after the reaction to obtain 3D COF@MAPbX 3 Composite materialMaterial preparation;
in S1, the first solvent is o-dichlorobenzene, n-butanol and 8-10M acetic acid, and BTD and Por-8NH are controlled 2 The mass volume ratio of TPDA, o-dichlorobenzene, n-butyl alcohol and acetic acid is 5-20 mg: 10-30 mg: 5-15 mg: 200-1000 [ mu ] L: 200-1000 [ mu ] L: 0-200 mu L;
in S2, the second solvent is N, N-dimethylformamide and ethanol, and the lead halide is one or a combination of a plurality of lead chloride, lead bromide and lead iodide; controlling the volume ratio of N, N-dimethylformamide to ethanol to be 1: 8-10, immersing the 3D COF material in the second solution, wherein the concentration of lead halide in the second solution is 0.8-1.2 mM;
in S3, the third solvent is ethanol, and the solubility of the methyl iodide in the third solvent is 0.8-1.2 mM.
Example 2: the preparation method of the three-dimensional covalent organic framework@metal halide perovskite composite material disclosed by the invention is different from that of the embodiment 1 in that the specific implementation mode of S1 is as follows,
firstly, 0.02mmol of BTD and 0.01mmol of Por-8NH are added 2 And 0.02mmol TPDA is put into a vacuum tube, 400 mu L of o-dichlorobenzene and 400 mu L of n-butanol are put into the vacuum tube, ultrasonic dispersion is carried out uniformly, 100 mu L of 9M acetic acid is put into the vacuum tube, the vacuum tube is subjected to freeze thawing and degassing for 3 times in 77K liquid nitrogen, the vacuum tube is sealed and reacts for 3 days at 120 ℃, after the reaction is finished, the vacuum tube is soaked in DMF solution at 60 ℃ for 3 times until the supernatant is colorless, the washing solid is extracted with acetone for 3 days, and then vacuum drying is carried out for 12 hours at 80 ℃ to obtain the 3D COF material.
Example 3: the preparation method of the three-dimensional covalent organic framework@metal halide perovskite composite material disclosed by the invention is different from that of the embodiment 1 in that the specific implementation mode of S1 is as follows,
firstly, 0.02mmol of BTD and 0.01mmol of Por-8NH are added 2 And 0.02mmol TPDA are put into a vacuum tube, 535 mu L o-dichlorobenzene and 265 mu L n-butanol are put into the vacuum tube, ultrasonic dispersion is uniform, 100 mu L9M acetic acid is put into the vacuum tube, the vacuum tube is frozen and thawed and degassed for 3 times in 77K liquid nitrogen, the vacuum tube is sealed and reacts for 3 days at 120 ℃, after the reaction is finished, the vacuum tube is soaked in DMF solution at 60 ℃ for 3 times repeatedly until the supernatant is colorless,and the washed solid is extracted with acetone for 3 days, and then vacuum dried for 12 hours at 80 ℃ to obtain the 3D COF material.
Example 4: the preparation method of the three-dimensional covalent organic framework@metal halide perovskite composite material disclosed by the invention is different from that of the embodiment 1 in that the specific implementation mode of S1 is as follows,
firstly, 0.02mmol of BTD and 0.01mmol of Por-8NH are added 2 And 0.02mmol TPDA is put into a vacuum tube, 640 mu L o-dichlorobenzene and 160 mu L n-butanol are put into the vacuum tube, ultrasonic dispersion is carried out uniformly, 100 mu L9M acetic acid is put into the vacuum tube, the vacuum tube is frozen and thawed and degassed 3 times in 77K liquid nitrogen, the vacuum tube is sealed and reacts for 3 days at 120 ℃, after the reaction is finished, the vacuum tube is soaked in DMF solution at 60 ℃ for 3 times until the supernatant is colorless, the washing solid is extracted with acetone for 3 days, and then vacuum drying is carried out for 12 hours at 80 ℃ to obtain the 3D COF material.
Example 5: the preparation method of the three-dimensional covalent organic framework@metal halide perovskite composite material disclosed by the invention is different from that of the embodiment 1 in that the specific implementation mode of S1 is as follows,
firstly, 0.02mmol of BTD and 0.01mmol of Por-8NH are added 2 And 0.02mmol TPDA is put into a vacuum tube, 900 mu L of o-dichlorobenzene and 100 mu L of n-butanol are put into the vacuum tube, ultrasonic dispersion is carried out uniformly, 100 mu L of 9M acetic acid is put into the vacuum tube, the vacuum tube is frozen and thawed and degassed 3 times in 77K liquid nitrogen, the vacuum tube is sealed and reacts for 3 days at 120 ℃, after the reaction is finished, the vacuum tube is soaked in DMF solution at 60 ℃ for 3 times until the supernatant is colorless, the washing solid is extracted with acetone for 3 days, and then vacuum drying is carried out for 12 hours at 80 ℃ to obtain the 3D COF material.
Example 6: the preparation method of the three-dimensional covalent organic framework@metal halide perovskite composite material disclosed by the invention is different from that of the embodiment 1 in that the specific implementation mode of S1 is as follows,
firstly, 0.02mmol of BTD and 0.01mmol of Por-8NH are added 2 And 0.02mmol TPDA are put into a vacuum tube, 480 mu L o-dichlorobenzene and 320 mu L n-butanol are put into the vacuum tube, the ultrasonic dispersion is uniform, 100 mu L9M acetic acid is put into the vacuum tube, the vacuum tube is frozen and thawed and degassed for 3 times in 77K liquid nitrogen, the vacuum tube is sealed and reacted for 3 days at 120 ℃, and after the reaction is finished, the vacuum tube is sealed and the vacuum tube is sealedIt was immersed in a DMF solution of 60 ℃ for 3 times until the supernatant was colorless, and the washed solid was soxhlet extracted with acetone for 3 days, followed by vacuum drying at 80 ℃ for 12 hours, to obtain a 3D COF material.
Example 7: the preparation method of the three-dimensional covalent organic framework@metal halide perovskite composite material disclosed by the invention is different from that of the embodiment 1 in that the specific implementation mode of S1 is as follows,
firstly, 0.02mmol of BTD and 0.01mmol of Por-8NH are added 2 And 0.02mmol TPDA is put into a vacuum tube, 265 mu L o-dichlorobenzene and 535 mu L n-butanol are put into the vacuum tube, ultrasonic dispersion is carried out uniformly, 100 mu L9M acetic acid is put into the vacuum tube, the vacuum tube is frozen and thawed and degassed 3 times in 77K liquid nitrogen, the vacuum tube is sealed and reacts for 3 days at 120 ℃, after the reaction is finished, the vacuum tube is soaked in DMF solution at 60 ℃ for 3 times until the supernatant is colorless, the washing solid is extracted with acetone for 3 days, and then vacuum drying is carried out for 12 hours at 80 ℃ to obtain the 3D COF material.
Example 8: the preparation method of the three-dimensional covalent organic framework@metal halide perovskite composite material disclosed by the invention is different from that of the embodiment 2 in that the specific implementation modes of S2-S3 are as follows,
s2 immersing the 3D COF material obtained in S1 into 1.0mM PbBr 2 PbBr in solution 2 The second solvent of the solution is in a volume ratio of 1:9 DMF and EtOH, soaking reaction for 1.0h to ensure PbBr 2 Fully enters a pore canal of a 3D COF material, after the reaction is finished, the reaction liquid is centrifuged, and the solid obtained by centrifugation is washed 3 times by pure ethanol to obtain the 3D COF@PbBr 2 A material;
s3, 3D COF@PbBr obtained by S2 2 Immersion of the material in 1.0mM CH 3 NH 3 In solution I, CH 3 NH 3 The third solvent of the solution I is ethanol, soaking reaction is carried out for 10min, after the reaction is finished, the solution I is washed by pure ethanol for 3 times, and vacuum drying is carried out for 6h at 50 ℃ to obtain 3D COF@MAPbBr 3 A composite material.
Example 9: the preparation method of the three-dimensional covalent organic framework@metal halide perovskite composite material disclosed by the invention is different from that of the embodiment 2 in that PbX 2 For PbI 2 Obtaining3D COF@MAPbI 3 A composite material.
Performance test
(1) After XRD detection of the 3D COF material prepared in example 2, the XRD data was imported into materials studio for Pawley refinement, and the results are shown in FIG. 4. As can be seen from fig. 4, the refined XRD data is substantially consistent with the simulated XRD peak shapes, indicating successful synthesis of such 3D COF materials.
(2) Determination of N at 77K for the 3D COF Material of example 2 in sequence 2 Adsorption-desorption isotherms of (c) and corresponding calculated pore size distribution of CO at different temperatures 2 The adsorption and desorption performance are shown in fig. 5-7. As can be seen from FIGS. 5 and 6, the BET specific surface area of the 3D COF material is 456.42m 2 g -1 Pore sizes were 3.28nm and 3.98nm. As can be seen from fig. 7, this 3D COF material is resistant to CO at different temperatures 2 All have certain adsorption capacity and are used for subsequent photocatalysis of CO 2 And (5) laying a foundation for reduction.
(3) The 3D COF@MAPbBr prepared in example 8 3 The composite material was subjected to an X-ray diffraction test, and the structure is shown in fig. 8. As can be seen from FIG. 8, 3D COF@MAPbBr 3 The composite material has 3D COF and MAPbBr at the same time 3 Further demonstrating the successful preparation of such composites.
(4) The 3D COF@MAPbBr prepared in example 8 3 Composite material, 3D COF@MAPbI prepared in example 9 3 The composite material was ultrasonically dispersed in absolute ethanol and subjected to Transmission Electron Microscopy (TEM) analysis, the results of which are shown in FIG. 9, wherein FIG. 9 (above) is 3D COF@MAPbI prepared in example 9 3 TEM image of composite material, FIG. 9 (below) shows 3D COF@MAPbBr obtained in example 8 3 TEM image of composite material. As can be seen from fig. 6 and 9, the average particle size of the perovskite quantum dots measured based on GMS 3 software was 3.02 nm and 3.09 nm, respectively, which is smaller than the pore size of the 3D COF, indicating successful in situ growth of the perovskite quantum dots within the COF pore channels.
(5) The 3D COF material of example 2 and the 3D COF@MAPbBr prepared in example 8 3 Composite material, example 93D COF@MAPbI 3 The composite material was subjected to an ultraviolet diffuse reflection test, and the result is shown in fig. 10. As can be seen from FIG. 10, the absorption strength of the composite material is significantly higher than that of pure COF, 3D COF@MAPbX 3 The light capturing capability of the composite is superior to that of the 3D COF materials.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention.
Claims (10)
1. A preparation method of a three-dimensional covalent organic framework@metal halide perovskite composite material is characterized by comprising the following steps of: comprises the steps of,
s1 in a first solvent, BTD and Por-8NH are added 2 Reacting with TPDA, and after the reaction is finished, performing post-treatment to obtain the 3D COF material;
s2, in a second solvent, reacting the 3D COF material obtained in the S1 with lead halide, and performing post-treatment after the reaction is finished to obtain the 3D COF@PbX 2 A material;
s3 in a third solvent, the 3D COF@PbX obtained by the S2 is prepared 2 Reacting the material with methyl iodide, and post-treating after the reaction to obtain 3D COF@MAPbX 3 A composite material.
2. The method for preparing a three-dimensional covalent organic framework @ metal halide perovskite composite material according to claim 1, wherein: in the step S1, the first solvent is o-dichlorobenzene, n-butanol and 8-10M acetic acid.
3. One kind of three according to claim 2The preparation method of the vitamin-covalent organic framework@metal halide perovskite composite material is characterized by comprising the following steps of: in the S1, BTD and Por-8NH are controlled 2 The mass volume ratio of TPDA, o-dichlorobenzene, n-butyl alcohol and acetic acid is 5-20 mg: 10-30 mg: 5-15 mg: 200-1000 [ mu ] L: 200-1000 [ mu ] L: 0-200 mu L.
4. A method of preparing a three-dimensional covalent organic framework @ metal halide perovskite composite material according to claim 3, wherein: in the S1, BTD and Por-8NH are firstly carried out 2 And TPDA is put into a vacuum tube, o-dichlorobenzene and n-butanol are put into the vacuum tube, ultrasonic dispersion is carried out uniformly, acetic acid is put into the vacuum tube, the vacuum tube is frozen and thawed and degassed for 2 to 4 times in 77K liquid nitrogen, the vacuum tube is sealed and reacts for 2 to 7 days at the temperature of 100 to 150 ℃, after the reaction is finished, the reactant is washed by DMF and/or acetone, the washing solid and the acetone are extracted for 1 to 3 days, and then the vacuum drying is carried out for 4 to 10 hours at the temperature of 50 to 120 ℃ to obtain the 3D COF material.
5. The method for preparing a three-dimensional covalent organic framework @ metal halide perovskite composite material according to claim 1, wherein: in the step S2, the second solvent is N, N-dimethylformamide and ethanol, and the lead halide is one or a combination of a plurality of lead chloride, lead bromide and lead iodide; controlling the volume ratio of N, N-dimethylformamide to ethanol to be 1: 8-10, immersing the 3D COF material in the second solution, and enabling the concentration of the lead halide in the second solution to be 0.8-1.2 mM.
6. The method for preparing a three-dimensional covalent organic framework @ metal halide perovskite composite material according to claim 5, wherein: in the S2, immersing the 3D COF material obtained in the S1 into PbX 2 And a second solvent, soaking the mixture for 0.5 to 1.5 hours to ensure PbX 2 Fully entering a pore canal of a 3D COF material, centrifuging the reaction liquid after the reaction is finished, washing the solid obtained by centrifugation with pure ethanol for 2-4 times to obtain the 3D COF@PbX 2 A material.
7. The method for preparing a three-dimensional covalent organic framework @ metal halide perovskite composite material according to claim 1, wherein: in the step S3, the third solvent is ethanol, and the solubility of the methyl iodide in the third solvent is 0.8-1.2 mM.
8. The method for preparing a three-dimensional covalent organic framework @ metal halide perovskite composite material according to claim 7, wherein: in the step S3, the 3D COF@PbX obtained in the step S2 is used for 2 Immersing the material into a solution of methyl iodide and a third solvent, carrying out an immersion reaction for 5-15 min, washing 2-4 times with pure ethanol after the reaction is finished, and carrying out vacuum drying for 4-10 h at 40-60 ℃ to obtain the 3D COF@MAPbX 3 A composite material.
9. A three-dimensional covalent organic framework @ metal halide perovskite composite material characterized by: the method for preparing the composite material according to any one of claims 1 to 8.
10. The application of the three-dimensional covalent organic framework@metal halide perovskite composite material is characterized in that: use of the three-dimensional covalent organic framework @ metal halide perovskite composite material prepared by the preparation method of any one of claims 1-8 in a photocatalyst.
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