CN114522543A - Ultrathin two-dimensional Cu-TCPP film and preparation method thereof - Google Patents
Ultrathin two-dimensional Cu-TCPP film and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
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- 239000000758 substrate Substances 0.000 claims abstract description 34
- 239000002135 nanosheet Substances 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000001652 electrophoretic deposition Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 13
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 26
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- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- SMOZAZLNDSFWAB-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,24-dihydroporphyrin-5-yl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(C=1C=CC(N=1)=C(C=1C=CC(=CC=1)C(O)=O)C1=CC=C(N1)C(C=1C=CC(=CC=1)C(O)=O)=C1C=CC(N1)=C1C=2C=CC(=CC=2)C(O)=O)=C2N=C1C=C2 SMOZAZLNDSFWAB-UHFFFAOYSA-N 0.000 claims description 2
- -1 4-carboxyphenyl Chemical group 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- RKCAIXNGYQCCAL-UHFFFAOYSA-N porphin Chemical compound N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RKCAIXNGYQCCAL-UHFFFAOYSA-N 0.000 claims description 2
- 238000001962 electrophoresis Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 35
- 239000012528 membrane Substances 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- 238000001728 nano-filtration Methods 0.000 description 6
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- 239000011148 porous material Substances 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- COXVTLYNGOIATD-HVMBLDELSA-N CC1=C(C=CC(=C1)C1=CC(C)=C(C=C1)\N=N\C1=C(O)C2=C(N)C(=CC(=C2C=C1)S(O)(=O)=O)S(O)(=O)=O)\N=N\C1=CC=C2C(=CC(=C(N)C2=C1O)S(O)(=O)=O)S(O)(=O)=O Chemical compound CC1=C(C=CC(=C1)C1=CC(C)=C(C=C1)\N=N\C1=C(O)C2=C(N)C(=CC(=C2C=C1)S(O)(=O)=O)S(O)(=O)=O)\N=N\C1=CC=C2C(=CC(=C(N)C2=C1O)S(O)(=O)=O)S(O)(=O)=O COXVTLYNGOIATD-HVMBLDELSA-N 0.000 description 2
- 239000001045 blue dye Substances 0.000 description 2
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/10—Testing of membranes or membrane apparatus; Detecting or repairing leaks
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/50—Control of the membrane preparation process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/04—Characteristic thickness
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention discloses a preparation method of an ultrathin two-dimensional Cu-TCPP film, which comprises the following steps: (1) pretreating the porous substrate; (2) the preparation concentration is 0.1-10 mg.L‑1Carrying out ultrasonic dispersion on the Cu-TCPP nanosheet alcoholic solution; (3) placing the porous substrate in the Cu-TCPP nano sheet alcohol solution in the step (1) for electrophoretic deposition to obtain a porous substrate covering the Cu-TCPP film; (4) and (4) drying the porous substrate covered with the Cu-TCPP film in the step (3) to obtain the ultrathin two-dimensional Cu-TCPP film. The method is simple, and the ultrathin two-dimensional Cu-TCPP film with the thickness of about 50-500 nm can be covered on the porous substrate through electrophoresis for 2-60 minutes.
Description
Technical Field
The invention belongs to the technical field of separation, and particularly relates to an ultrathin two-dimensional Cu-TCPP (copper-TCPP) membrane and a preparation method thereof.
Background
Industrial separation/purification is a very energy-consuming process, with the energy consumed for separation accounting for 15% of the total energy consumption worldwide. For subcritical mixtures, the separation technique that is currently widely employed is distillation. However, despite the simpler operating principle of distillation, such a separation based on volatility requires a large amount of thermal energy, which makes the technology less energy efficient. It has been shown by data that if advanced membrane separation techniques were used instead of conventional distillation, the energy consumption would be reduced by 90% under the same conditions.
Metal Organic Frameworks (MOFs) are a class of crystalline porous materials in which metal ions and organic ligands are linked by coordination bonds to form one-, two-, or three-dimensional periodic networks. Due to the various structures, high surface area and adsorption behavior, the composite material has good application prospect in the fields of membrane separation and the like. The MOF nanosheet is a novel two-dimensional material, and can provide accurate molecular size identification due to the nanometer-sized thickness, a large number of regular pore arrays and stable interlayer channels, so that the MOF nanosheet is expected to become a candidate material for preparing a super-pore-size and high-selectivity membrane. However, to date, there are few reported methods for rapidly constructing two-dimensional MOF films, and the films are prepared by using conventional suction filtration, hot drop coating and the like. However, both of these methods have problems such as generation of defects that easily cause a film, a long preparation time, and possibility of damaging the nanosheet structure. There is therefore a great need to develop a method for rapidly synthesizing two-dimensional MOF ultrathin films.
Disclosure of Invention
In order to solve the disadvantages and shortcomings of the prior art, the invention provides a method for preparing an ultrathin two-dimensional Cu-TCPP film.
The second purpose of the invention is to provide the ultrathin two-dimensional Cu-TCPP film prepared by the preparation method, wherein the ultrathin two-dimensional Cu-TCPP film is prepared by an electrophoretic deposition method.
The primary purpose of the invention is realized by the following technical scheme:
a preparation method of an ultrathin two-dimensional Cu-TCPP film comprises the following steps:
(1) pretreating the porous substrate;
(2) the preparation concentration is 0.1-10 mg.L-1Subjecting the Cu-TCPP nanosheet alcoholic solution to ultrasonic treatmentDispersing;
(3) placing the porous substrate in the Cu-TCPP nano sheet alcohol solution in the step (2) for electrophoretic deposition to obtain a porous substrate covering the Cu-TCPP film;
(4) and (4) drying the porous substrate covered with the Cu-TCPP film in the step (3) to obtain the ultrathin two-dimensional Cu-TCPP film.
Preferably, the porous substrate described in step (1) refers to porous Anodized Aluminum (AAO).
Preferably, the pretreatment method described in step (1) comprises ethanol washing and drying.
Preferably, the preparation method of the Cu-TCPP nanosheet alcoholic solution in step (2) is:
(a) dissolving copper nitrate trihydrate, trifluoroacetic acid and polyvinylpyrrolidone in a mixed solvent of N, N-dimethylformamide and ethanol;
(b) dissolving meso-tetra (4-carboxyphenyl) porphin (TCPP) in a mixed solvent of N, N-dimethylformamide and ethanol;
(c) dripping the mixed solution prepared in the step (b) into the mixed solution prepared in the step (a) while stirring, performing ultrasonic reaction for 10-30min, performing reaction for 2-6h at 70-90 ℃, and centrifuging for 5-20min under the conditions of 8000-12000 rpm;
(d) washing the nanosheet obtained by centrifugation in the step (c) twice by using ethanol, and centrifuging for 5-20min under the washing condition of 8000-10000 rpm;
(e) and (d) dispersing and storing the nanosheets obtained in the step (d) again by using ethanol to obtain a Cu-TCPP nanosheet alcoholic solution.
Preferably, the volume ratio of the N, N-dimethylformamide to the ethanol in the mixture of N, N-dimethylformamide and ethanol described in step (a) is 3: 1.
Preferably, the molar ratio of copper nitrate trihydrate as described in step (a) to meso-tetra (4-carboxyphenyl) porphine (TCPP) as described in step (b) is 3: 1.
Preferably, the ultrasonic dispersion frequency in the step (2) is 20-100 kHz, and the ultrasonic time is 20-70 min.
Preferably, the ultrasonic dispersion frequency in the step (2) is 40-70 kHz, and the ultrasonic time is 30-60 min.
Preferably, the electrophoretic deposition in the step (3) is to insert a porous substrate and positive and negative electrodes into the Cu-TCPP nanosheet solution, the porous substrate is located at the middle position of the positive and negative electrodes, the voltage of the electrophoretic deposition is 10V to 36V of direct current voltage, and the time of the electrophoretic deposition is 2 to 60 min.
Preferably, the drying in the step (4) is drying in the air at room temperature, and the drying time is 6-24 h.
The second purpose of the invention is realized by the following technical scheme:
an ultrathin two-dimensional Cu-TCPP film is prepared by the preparation method.
Preferably, the thickness of the ultrathin two-dimensional Cu-TCPP film is 50-500 nm.
Preferably, the thickness of the ultrathin two-dimensional Cu-TCPP film is 140-340 nm.
Compared with the prior art, the invention has the following advantages:
(1) the preparation method of the two-dimensional Cu-TCPP film greatly shortens the time for preparing the film, promotes the film to grow a compact film layer in a very short time, and provides possibility for the subsequent large-scale production of the two-dimensional Cu-TCPP film;
(2) the preparation method of the two-dimensional Cu-TCPP film has the advantages of simple operation, controllable thickness and good continuity;
(3) the thickness of the two-dimensional Cu-TCPP film prepared by the method is 50-500 mm, and the ion rejection rate is up to more than 98.86%.
Drawings
FIG. 1 is a scanning electron microscope image of the front side of an ultra-thin two-dimensional Cu-TCPP film in example 1;
fig. 2 is a scanning electron microscope image of a cross section of the ultra-thin two-dimensional Cu-TCPP film in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1:
a preparation method of a Cu-TCPP nanosheet alcoholic solution comprises the following steps:
(a) copper nitrate trihydrate (3.6mg,0.015mmol), (1.0 M.times.10. mu.L) trifluoroacetic acid, and (10.0mg) polyvinylpyrrolidone were dissolved in a mixed solvent of (9ml) N, N-dimethylformamide and (3ml) ethanol;
(b) dissolving (4.0mg,0.005mmol) meso-tetrakis (4-carboxyphenyl) porphine (TCPP) in a mixed solvent of (3ml) N, N-dimethylformamide and (1ml) ethanol;
(c) dripping the mixed solution prepared in the step (b) into the mixed solution prepared in the step (a) while stirring, performing ultrasonic treatment for 20min, reacting for 3h at 80 ℃, and centrifuging for 10min under the condition of 10000 rpm;
(d) washing the nanosheet obtained by centrifuging in the step (c) twice by using ethanol, and centrifuging for 10min under the washing condition of 10000 rpm;
(e) and (d) dispersing and storing the nanosheets obtained in the step (d) again by using ethanol to prepare the Cu-TCPP nanosheet alcoholic solution.
The concentration of each of the solutions was 1.0 mg.L-1An alcoholic solution of Cu-TCPP nanosheet of 1.5 mg.L-1The Cu-TCPP nano-sheet alcoholic solution and 1.8 mg.L-1The Cu-TCPP nano-sheet alcoholic solution.
Example 2:
a preparation method of an ultrathin two-dimensional Cu-TCPP film comprises the following steps:
(1) washing porous Anodic Aluminum Oxide (AAO) with the pore diameter distribution of 160-200nm and the diameter of 12mm by using ethanol, and drying in a 60 ℃ drying oven.
(2) 30mL of the solution prepared in example 1 was taken and the concentration was 1.0 mg. L-1And (3) carrying out ultrasonic treatment on the Cu-TCPP nano sheet alcohol solution for 30min at 60 kHz.
(3) Inserting a porous substrate and positive and negative electrodes into the Cu-TCPP nano sheet alcohol solution, wherein the porous substrate is positioned in the middle of the positive and negative electrodes, the voltage of electrophoretic deposition is 25V direct current voltage, and the time of electrophoretic deposition is 10 min.
(4) And (4) drying the porous substrate covered with the Cu-TCPP film in the step (3) for 6 hours at room temperature to obtain the ultrathin two-dimensional Cu-TCPP film.
And (4) performing scanning electron microscope characterization on the substrate in the step (4) to obtain a front-side micro-topography map as shown in figure 1, a cross-section micro-topography map as shown in figure 2, wherein the surface of the substrate is covered with a compact Cu-TCPP film, the cross section of the substrate has an obvious layered structure, and the thickness of the substrate is about 200 nm.
Nanofiltration separation performance test of the membrane prepared in this example: placing the membrane in a nanofiltration testing device, selecting Congo red dye (2.56 × 0.73nm, concentration 20mg/L), and water flux of 3.197 L.m-2·h-1·bar-1The rejection was 98.86%.
Example 3:
a preparation method of an ultrathin two-dimensional Cu-TCPP film comprises the following steps:
(1) washing porous Anodic Alumina (AAO) with the pore size distribution of 160-200nm and the diameter of 12mm by using ethanol, and drying in an oven at 60 ℃.
(2) 30mL of the solution prepared in example 1 with the concentration of 1.5 mg. L-1The Cu-TCPP nano sheet alcoholic solution is subjected to ultrasonic treatment for 50min at 40 kHz.
(3) Inserting a porous substrate and positive and negative electrodes into the Cu-TCPP nano sheet alcohol solution, wherein the porous substrate is positioned in the middle of the positive and negative electrodes, the voltage of electrophoretic deposition is 30V direct current voltage, and the time of electrophoretic deposition is 2 min.
(4) And (4) drying the porous substrate covered with the Cu-TCPP film in the step (3) at room temperature for 12h to obtain the ultrathin two-dimensional Cu-TCPP film.
And (4) performing scanning electron microscope characterization on the substrate in the step (4), and observing the covered ultrathin Cu-TCPP film with the thickness of about 140 nm.
Nanofiltration separation performance test of the membrane prepared in this example: placing the membrane in a nanofiltration testing device, selecting Evans blue dye (3.10 × 1.20nm, concentration 20mg/L), and water flux of 6.30 L.m-2·h-1·bar-1The retention rate was 96.44%.
Example 4:
a preparation method of an ultrathin two-dimensional Cu-TCPP film comprises the following steps:
(1) washing porous Anodic Aluminum Oxide (AAO) with pore size distribution of 160-200nm and diameter of 15mm by using ethanol, and drying in a 60 ℃ drying oven;
(2) 40mL of the solution prepared in example 1 and having a concentration of 1.8 mg. L-1Performing ultrasonic treatment on the Cu-TCPP nano sheet alcohol solution for 60min at 70 kHz;
(3) inserting a porous substrate and positive and negative electrodes into a Cu-TCPP nano sheet alcohol solution, wherein the porous substrate is positioned in the middle of the positive and negative electrodes, the voltage of electrophoretic deposition is 36V direct current voltage, and the time of electrophoretic deposition is 20 min;
(4) and (4) drying the porous substrate covered with the Cu-TCPP film in the step (3) for 24 hours at room temperature to obtain the ultrathin two-dimensional Cu-TCPP film.
And (4) performing scanning electron microscope characterization on the substrate in the step (4), and observing the covered ultrathin Cu-TCPP film with the thickness of about 320 nm.
Nanofiltration separation performance test of the membrane prepared in this example: placing the membrane in a nanofiltration testing device, selecting Evans blue dye (3.10 × 1.20nm, concentration 20mg/L), and water flux of 0.32 L.m-2·h-1·bar-1The rejection was 99.80%.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The preparation method of the ultrathin two-dimensional Cu-TCPP film is characterized by comprising the following steps of:
(1) pretreating the porous substrate;
(2) the preparation concentration is 0.1-10 mg.L-1Carrying out ultrasonic dispersion on the Cu-TCPP nano sheet alcohol solution;
(3) placing the porous substrate in the Cu-TCPP nano sheet alcohol solution in the step (1) for electrophoretic deposition to obtain a porous substrate covering the Cu-TCPP film;
(4) and (4) drying the porous substrate covered with the Cu-TCPP film in the step (3) to obtain the ultrathin two-dimensional Cu-TCPP film.
2. The method for preparing the ultrathin two-dimensional Cu-TCPP film as claimed in claim 1, wherein the porous substrate in the step (1) is porous anodized aluminum.
3. The method for preparing the ultra-thin two-dimensional Cu-TCPP film according to claim 1, wherein the pretreatment in the step (1) comprises ethanol washing and drying.
4. The preparation method of the ultrathin two-dimensional Cu-TCPP film as claimed in claim 1, wherein the ultrasonic dispersion frequency in step (2) is 20-100 kHz, and the ultrasonic time is 20-70 min.
5. The method for preparing the ultrathin two-dimensional Cu-TCPP film according to claim 1, wherein the method for preparing the Cu-TCPP nano-sheet alcoholic solution in the step (2) is as follows:
(a) dissolving copper nitrate trihydrate, trifluoroacetic acid and polyvinylpyrrolidone in a mixed solvent of N, N-dimethylformamide and ethanol;
(b) dissolving meso-tetra (4-carboxyphenyl) porphin in a mixed solvent of N, N-dimethylformamide and ethanol;
(c) dripping the mixed solution prepared in the step (b) into the mixed solution prepared in the step (a) while stirring, performing ultrasonic reaction for 10-30min, performing reaction for 2-6h at 70-90 ℃, and centrifuging for 5-20min under the conditions of 8000-12000 rpm;
(d) washing the nanosheet obtained by centrifugation in the step (c) twice by using ethanol, and centrifuging for 5-20min under the washing condition of 8000-10000 rpm;
(e) and (d) dispersing and storing the nanosheets obtained in the step (d) by using ethanol again.
6. The method for preparing an alcoholic solution of Cu-TCPP nanosheets according to claim 5, wherein the volume ratio of N, N-dimethylformamide to ethanol in the mixture of N, N-dimethylformamide and ethanol in step (a) is 3: 1.
7. The method for preparing an alcoholic solution of Cu-TCPP nanosheet of claim 5, wherein the molar ratio of copper nitrate trihydrate in step (a) to meso-tetra (4-carboxyphenyl) porphine in step (b) is 3: 1.
8. The preparation method of the ultrathin two-dimensional Cu-TCPP film as claimed in claim 1, wherein the electrophoretic deposition in step (3) is to insert a porous substrate and positive and negative electrodes into the Cu-TCPP nanosheet solution, the porous substrate is in the middle position of the positive and negative electrodes, the voltage of the electrophoretic deposition is 10V-36V direct current voltage, and the time of the electrophoretic deposition is 2-60 min.
9. An ultra-thin two-dimensional Cu-TCPP film prepared by the method of any one of claims 1 to 8.
10. The ultrathin two-dimensional Cu-TCPP film according to claim 9, wherein the ultrathin two-dimensional Cu-TCPP film has a thickness of 50 to 500 nm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115627003A (en) * | 2022-09-29 | 2023-01-20 | 军事科学院军事医学研究院环境医学与作业医学研究所 | MOF-on-MOF composite membrane material and preparation method thereof |
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| CN115999641A (en) * | 2022-08-29 | 2023-04-25 | 山东万博环境治理有限公司 | CeO (CeO) 2 Cu-TCPP composite photocatalyst and preparation method and application thereof |
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| CN115627003A (en) * | 2022-09-29 | 2023-01-20 | 军事科学院军事医学研究院环境医学与作业医学研究所 | MOF-on-MOF composite membrane material and preparation method thereof |
| CN115627003B (en) * | 2022-09-29 | 2023-08-18 | 军事科学院军事医学研究院环境医学与作业医学研究所 | MOF-on-MOF composite membrane material and preparation method thereof |
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