CN116672900B - Preparation method and application of super-hydrophobic copper mesh/covalent organic polymer composite film - Google Patents
Preparation method and application of super-hydrophobic copper mesh/covalent organic polymer composite film Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 107
- 239000010949 copper Substances 0.000 title claims abstract description 107
- 229920000620 organic polymer Polymers 0.000 title claims abstract description 65
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000926 separation method Methods 0.000 claims abstract description 28
- 238000012986 modification Methods 0.000 claims abstract description 22
- 230000004048 modification Effects 0.000 claims abstract description 22
- 239000012528 membrane Substances 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 40
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 34
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 230000004907 flux Effects 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 239000002897 polymer film coating Substances 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 3
- 235000019476 oil-water mixture Nutrition 0.000 abstract description 3
- 239000002262 Schiff base Substances 0.000 abstract 1
- 150000004753 Schiff bases Chemical class 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 description 18
- 239000000843 powder Substances 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 235000019198 oils Nutrition 0.000 description 12
- 238000002791 soaking Methods 0.000 description 12
- KQIKKETXZQDHGE-UHFFFAOYSA-N 4-[(4-aminophenyl)diazenyl]aniline Chemical compound C1=CC(N)=CC=C1N=NC1=CC=C(N)C=C1 KQIKKETXZQDHGE-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/022—Metals
-
- 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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a preparation method and application of a super-hydrophobic copper mesh/covalent organic polymer composite membrane, wherein the composite membrane can be used for oil-water separation; the preparation method comprises the following steps: a) Pretreatment of a copper mesh substrate; b) Modification of a copper mesh substrate; c) Growing a super-hydrophobic covalent organic polymer on a copper mesh in situ based on a Schiff base reaction; d) The prepared super-hydrophobic copper mesh/covalent organic polymer composite membrane can be used for high-efficiency separation of various oil-water mixed solutions. The preparation method is simple and environment-friendly, the used reagent does not need to be further purified, and the prepared super-hydrophobic copper mesh/covalent organic polymer composite membrane has excellent oil-water separation effect and circulation stability on various oil-water mixtures.
Description
Technical Field
The invention relates to the field of oily sewage treatment, in particular to a preparation method and application of a super-hydrophobic copper mesh/covalent organic polymer composite membrane.
Background
Along with the continuous development of science and technology, the living standard of people is also continuously improved. And environmental pollution problems are becoming more and more of a concern. Water and oil pollution exists in both the exploitation and transportation process of fossil fuel and the catering industry and the food processing industry. For the water environment pollution problem, especially for the oil pollution, the oil-water separation by adopting the filtering technology has been widely studied. Therefore, the research on the novel super-hydrophobic nano composite membrane solves the problem of pollution of oily wastewater and is a global environmental treatment subject.
Covalent organic polymers are organic porous materials which are formed by completely connecting light elements (C, B, O, N and the like) through covalent bonds, and the covalent organic polymer films have better application potential in the fields of ion transmission, oily sewage treatment and the like due to the characteristics of abundant synthetic routes, excellent stability, high specific surface area and easiness in modification. The super-hydrophobic polymer coated sponge and polyester fabrics reported at present have been successfully synthesized [1,2] And is used for preparing oil-water separation materials, but has lower permeation flux and poor antifouling performance. However, the separation of the oil-water mixture using the net is greatly advantageous compared with other separation methods because it is more convenient, has high flux and has high separation efficiency. Therefore, the development of the super-hydrophobic copper mesh/covalent organic polymer composite membrane with simple preparation method, excellent oil-water separation effect and good cycle stability has great significance for solving the practical problem of pollution of oily wastewater.
Disclosure of Invention
The invention provides a preparation method and application of a super-hydrophobic copper mesh/covalent organic polymer composite membrane, which comprises the steps of firstly, preprocessing a substrate to remove organic matters and other impurities on the surface, then, modifying the copper mesh by 3-aminopropyl triethoxysilane, then, preparing trimellitic aldehyde solution with the same concentration and taking dimethyl sulfoxide as a solvent, mixing the trimellitic aldehyde solution with 4,4' -azobisidine according to the volume ratio, adding 1 mu L of octanoic acid, carrying out ultrasonic mixing for 10min, placing the processed copper mesh therein, and reacting for 36 hours at 120 ℃ by a repeated growth method to obtain the super-hydrophobic covalent organic polymer loaded on the copper mesh. The composite membrane has good oil-water separation capability.
The aim of the invention is achieved by the following technical proposal
The preparation method of the super-hydrophobic copper mesh/covalent organic polymer composite film comprises the following specific steps:
step 1: preparation of superhydrophobic covalent organic polymer powders
Preparing trimellitic aldehyde and 4,4' -azobisiniline solutions with the concentration of 0.05mol/L-0.12mol/L respectively by taking dimethyl sulfoxide as a solvent, mixing the two solutions according to the volume ratio, adding 1 mu L of octanoic acid, carrying out ultrasonic treatment for 10min, transferring into a reaction kettle, heating at 120 ℃ for 12 hours, filtering and separating the generated precipitate, and sequentially cleaning the precipitate by acetone and tetrahydrofuran respectively and drying to obtain super-hydrophobic covalent organic polymer powder;
step 2: preparation of super-hydrophobic copper net/covalent organic polymer composite film
2.1: pretreatment of copper mesh
Sequentially ultrasonically cleaning with acetone, ethanol and 1mol/L hydrochloric acid for 10min, removing impurities such as oil stains on the surface, finally ultrasonically cleaning the solvent on the surface of the copper mesh in deionized water for 10min, and drying for later use.
2.2: 3-aminopropyl triethoxysilane modification of substrates
The copper mesh dried in 2.1 was treated with 3-aminopropyl triethoxysilane at 110 ℃ for 2 hours, washed with ethanol and dried.
2.3: trimesic aldehyde modification of further substrates
The copper mesh modified with 3-aminopropyl triethoxysilane was treated with trimesic aldehyde at 80 ℃ for 2 hours and dried for use.
2.4: copper net of super-hydrophobic covalent organic polymer film coating is synthesized by repeated growth method
Preparing trimellitic aldehyde and 4,4' -azobisiniline solution with concentration of 0.01mol/L-0.03mol/L respectively by taking dimethyl sulfoxide as a solvent, mixing the two solutions according to the volume ratio, slowly adding 1 mu L of octanoic acid which is not further purified as a catalyst, putting the copper mesh dried in 2.3 into the reaction solution, synthesizing at 120 ℃ for 12 hours, pouring out the solution, and adding another fresh synthetic solution with the same concentration into an autoclave for repeated synthesis. Repeating the steps for three times to obtain a copper net with the final modification time of 36 hours, taking out the copper net, washing the copper net with acetone and tetrahydrofuran, and drying the copper net to obtain the copper net loaded with the super-hydrophobic covalent organic polymer film.
The invention further provides a preparation method of the super-hydrophobic copper mesh/covalent organic polymer composite film, and the super-hydrophobic covalent organic polymer composite film loaded on the copper mesh is prepared.
Furthermore, the invention also provides application of the super-hydrophobic copper mesh/covalent organic polymer composite membrane in separating organic matters from water mixtures.
Further, the super-hydrophobic copper mesh/covalent organic polymer composite membrane can separate mutually-insoluble liquid organic matters and water through filtration at normal temperature, and the oil flux is at least 60L/(m) 2 S) in the cycle of 50 times of oil-water separation, the separation efficiency still reaches more than 98%, and the separation efficiency is stable.
Drawings
For a clearer description of one or more embodiments of the present description or of the solutions of the prior art, the drawings that are necessary for the description of the embodiments or of the prior art will be briefly described, it being apparent that the drawings in the description below are only one or more embodiments of the present description, from which other drawings can be obtained, without inventive effort, for a person skilled in the art.
FIG. 1 is a synthetic route diagram of the superhydrophobic covalent organic polymer powder prepared in example 1 of the invention;
FIG. 2 is an infrared spectrum of the superhydrophobic covalent organic polymer powder prepared in example 1 of the invention;
FIG. 3 is an SEM image of a superhydrophobic copper mesh/covalent organic polymer composite film prepared according to example 1 of the invention;
FIG. 4 is a graph showing the water contact angle of the super-hydrophobic copper mesh/covalent organic polymer composite film according to example 1 of the present invention;
FIG. 5 is a graph showing the efficiency of oil-water separation and flow rate of the super-hydrophobic copper mesh/covalent organic polymer composite film in example 4 of the present invention.
FIG. 6 is a graph showing the reproducibility of oil-water separation of the super-hydrophobic copper mesh/covalent organic polymer composite film in example 4 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments thereof in order to make the objects, technical solutions and advantages of the present disclosure more apparent.
Example 1
Preparation of superhydrophobic covalent organic polymer powders
Step 1: preparation of superhydrophobic covalent organic polymer powders
Trimesic aldehyde is dispersed in dimethyl sulfoxide to obtain 0.075mol/L suspension, 4' -azobis aniline is dispersed in dimethyl sulfoxide to obtain 0.075mol/L solution, and two solutions with the same concentration are mixed with 2:3, adding 1 mu L of octanoic acid, carrying out ultrasonic treatment for 10min, transferring into a reaction kettle, heating at 120 ℃ for 12 h, filtering and separating generated precipitate, soaking the precipitate twice with acetone, changing each time for 24 h, then washing with tetrahydrofuran by the same method, and finally drying the washed precipitate at 80 ℃ for 24 h to obtain orange super-hydrophobic covalent organic polymer powder (0.03982 g, yield is 81.6%); the synthetic route diagram is shown in figure 1, and the infrared spectrogram is shown in figure 2;
step 2: preparation of 250-mesh super-hydrophobic copper mesh/covalent organic polymer composite film
Step 2.1: pretreatment of copper mesh
Sequentially soaking a round copper mesh with the diameter of 3cm and 250 meshes with acetone, ethanol and 1mol/L hydrochloric acid, ultrasonically cleaning for 10min, removing impurities such as oil stains on the surface, finally soaking in deionized water, ultrasonically cleaning a solvent on the surface of the copper mesh for 10min, and drying for later use.
Step 2.2: 3-aminopropyl triethoxysilane modification of substrates
The copper mesh dried in step 2.1 was treated with 3-aminopropyl triethoxysilane (0.5 g in 20mL toluene) at 110 ℃ for 2 hours, washed with ethanol and dried.
Step 2.3: trimesic aldehyde modification of further substrates
The copper mesh modified with 3-aminopropyl triethoxysilane was treated with trimesic aldehyde (0.012 g in 10ml of 1, 4-dioxane) at 80 ℃ for 2 hours and dried for use.
Step 2.4: copper net of super-hydrophobic covalent organic polymer coating synthesized by repeated growth method
The trimesic aldehyde is dispersed in dimethyl sulfoxide to obtain 0.024mol/L solution, the 4,4' -azobis aniline is dispersed in dimethyl sulfoxide to obtain 0.024mol/L solution, the two solutions with the same concentration are mixed with each other in a volume of 2:3, 1 mu L of octanoic acid which is not further purified is slowly added as a catalyst, the copper mesh dried in the step 2.3 is placed into the reaction solution for synthesis at 120 ℃ for 12 hours, the solution is poured out, and the other fresh synthesis solution with the same concentration is added into an autoclave for repeated synthesis. The process is repeated three times, finally, the copper net with the modification time of 36 hours is obtained, the copper net is taken out, washed by acetone and tetrahydrofuran and dried, and the copper net loaded with the super-hydrophobic covalent organic polymer film is obtained, and the SEM diagram is shown in figure 3.
Example 2
Step 1: preparation of superhydrophobic covalent organic polymer powders
Trimesic aldehyde is dispersed in dimethyl sulfoxide to obtain 0.075mol/L suspension, 4' -azobis aniline is dispersed in dimethyl sulfoxide to obtain 0.075mol/L solution, and two solutions with the same concentration are mixed with 2:3, adding 1 mu L of octanoic acid, carrying out ultrasonic treatment for 10min, transferring into a reaction kettle, heating at 120 ℃ for 12 h, filtering and separating generated precipitate, soaking the precipitate twice with acetone, changing each time for 24 h, then washing with tetrahydrofuran by the same method, and finally drying the washed precipitate at 80 ℃ for 24 h to obtain orange super-hydrophobic covalent organic polymer powder.
Step 2: preparation of 300-mesh super-hydrophobic copper mesh/covalent organic polymer composite membrane
Step 2.1: pretreatment of copper mesh
Sequentially soaking a round copper mesh with the diameter of 3cm and 300 meshes with acetone, ethanol and 1mol/L hydrochloric acid, ultrasonically cleaning for 10min, removing impurities such as oil stains on the surface, finally soaking in deionized water, ultrasonically cleaning a solvent on the surface of the copper mesh for 10min, and drying for later use.
Step 2.2: 3-aminopropyl triethoxysilane modification of substrates
The copper mesh dried in step 2.1 was treated with 3-aminopropyl triethoxysilane (0.5 g in 20mL toluene) at 110 ℃ for 2 hours, washed with ethanol and dried.
Step 2.3: trimesic aldehyde modification of further substrates
The copper mesh modified with 3-aminopropyl triethoxysilane was treated with trimesic aldehyde (0.012 g in 10ml of 1, 4-dioxane) at 80 ℃ for 2 hours and dried for use.
Step 2.4: copper net of super-hydrophobic covalent organic polymer coating synthesized by repeated growth method
The trimesic aldehyde is dispersed in dimethyl sulfoxide to obtain 0.024mol/L solution, the 4,4' -azobis aniline is dispersed in dimethyl sulfoxide to obtain 0.024mol/L solution, the two solutions with the same concentration are mixed with each other in a volume of 2:3, 1 mu L of octanoic acid which is not further purified is slowly added as a catalyst, the copper mesh dried in the step 2.3 is placed into the reaction solution for synthesis at 120 ℃ for 12 hours, the solution is poured out, and the other fresh synthesis solution with the same concentration is added into an autoclave for repeated synthesis. And repeating the steps for three times to finally obtain the copper net with the modification time of 36 hours, taking out the copper net, washing the copper net with acetone and tetrahydrofuran, and drying the copper net to obtain the copper net loaded with the super-hydrophobic covalent organic polymer film.
Example 3
Step 1: preparation of superhydrophobic covalent organic polymer powders
Dispersing trimesic aldehyde in dimethyl sulfoxide to obtain a suspension of 0.075mol/L, dispersing 4,4' -azobis-aniline in dimethyl sulfoxide to obtain a solution of 0.075mol/L, mixing the two solutions with the same concentration in a volume of 2:3, adding 1 mu L of octanoic acid, carrying out ultrasonic treatment for 10min, transferring to a reaction kettle, heating at 120 ℃ for 12 hours, filtering and separating a generated precipitate, soaking the precipitate in acetone twice for 24 hours each, replacing the precipitate with one time, washing the precipitate with tetrahydrofuran by the same method, and finally drying the washed precipitate at 80 ℃ for 24 hours to obtain orange super-hydrophobic covalent organic polymer powder.
Step 2: preparation of 200-mesh super-hydrophobic copper mesh/covalent organic polymer composite film
Step 2.1: pretreatment of copper mesh
Sequentially soaking a round copper mesh with the diameter of 3cm and 200 meshes with acetone, ethanol and 1mol/L hydrochloric acid, ultrasonically cleaning for 10min, removing impurities such as oil stains on the surface, finally soaking in deionized water, ultrasonically cleaning a solvent on the surface of the copper mesh for 10min, and drying for later use.
Step 2.2: 3-aminopropyl triethoxysilane modification of substrates
The copper mesh dried in step 2.1 was treated with 3-aminopropyl triethoxysilane (0.5 g in 20mL toluene) at 110 ℃ for 2 hours, washed with ethanol and dried.
Step 2.3: trimesic aldehyde modification of further substrates
The copper mesh modified with 3-aminopropyl triethoxysilane was treated with trimesic aldehyde (0.012 g in 10ml of 1, 4-dioxane) at 80 ℃ for 2 hours and dried for use.
Step 2.4: copper net of super-hydrophobic covalent organic polymer coating synthesized by repeated growth method
The trimesic aldehyde is dispersed in dimethyl sulfoxide to obtain 0.024mol/L solution, the 4,4' -azobis aniline is dispersed in dimethyl sulfoxide to obtain 0.024mol/L solution, the two solutions with the same concentration are mixed with each other in a volume of 2:3, 1 mu L of octanoic acid which is not further purified is slowly added as a catalyst, the copper mesh dried in the step 2.3 is placed into the reaction solution for synthesis at 120 ℃ for 12 hours, the solution is poured out, and the other fresh synthesis solution with the same concentration is added into an autoclave for repeated synthesis. And repeating the steps for three times to finally obtain the copper net with the modification time of 36 hours, taking out the copper net, washing the copper net with acetone and tetrahydrofuran, and drying the copper net to obtain the copper net loaded with the super-hydrophobic covalent organic polymer film.
Example 4
Step 1 preparation of superhydrophobic covalent organic Polymer powder
Dispersing trimesic aldehyde in dimethyl sulfoxide to obtain a suspension of 0.075mol/L, dispersing 4,4' -azobis-aniline in dimethyl sulfoxide to obtain a solution of 0.075mol/L, mixing the two solutions with the same concentration in a volume of 2:3, adding 1 mu L of octanoic acid, carrying out ultrasonic treatment for 10min, transferring to a reaction kettle, heating at 120 ℃ for 12 hours, filtering and separating a generated precipitate, soaking the precipitate in acetone twice for 24 hours each, replacing the precipitate with one time, washing the precipitate with tetrahydrofuran by the same method, and finally drying the washed precipitate at 80 ℃ for 24 hours to obtain orange super-hydrophobic covalent organic polymer powder.
Step 2, preparation of 250-mesh super-hydrophobic copper mesh/covalent organic polymer composite film
Step 2.1: pretreatment of copper mesh
Sequentially soaking a round copper mesh with the diameter of 3cm and 250 meshes with acetone, ethanol and 1mol/L hydrochloric acid, ultrasonically cleaning for 10min, removing impurities such as oil stains on the surface, finally soaking in deionized water, ultrasonically cleaning a solvent on the surface of the copper mesh for 10min, and drying for later use.
Step 2.2: 3-aminopropyl triethoxysilane modification of substrates
The copper mesh dried in step 2.1 was treated with 3-aminopropyl triethoxysilane (0.5 g in 20mL toluene) at 110 ℃ for 2 hours, washed with ethanol and dried.
Step 2.3: trimesic aldehyde modification of further substrates
The copper mesh modified with 3-aminopropyl triethoxysilane was treated with trimesic aldehyde (0.012 g in 10ml of 1, 4-dioxane) at 80 ℃ for 2 hours and dried for use.
Step 2.4: copper net of super-hydrophobic covalent organic polymer coating synthesized by repeated growth method
The trimesic aldehyde is dispersed in dimethyl sulfoxide to obtain 0.036mol/L solution, the 4,4' -azobis aniline is dispersed in dimethyl sulfoxide to obtain 0.036mol/L solution, the two solutions with the same concentration are mixed in a volume of 2:3, 1 mu L of octanoic acid which is not further purified is slowly added as a catalyst, the copper mesh dried in the step 2.3 is placed into the reaction solution for synthesis at 120 ℃ for 12 hours, the solution is poured out, and the other fresh synthesis solution with the same concentration is added into an autoclave for repeated synthesis. And repeating the steps for three times to finally obtain the copper net with the modification time of 36 hours, taking out the copper net, washing the copper net with acetone and tetrahydrofuran, and drying the copper net to obtain the copper net loaded with the super-hydrophobic covalent organic polymer film.
Microstructure characterization and oil-water separation performance detection of super-hydrophobic covalent organic polymer powder and super-hydrophobic copper net/covalent organic polymer composite film
The method comprises the steps of adopting Fourier transform infrared analysis raw materials to synthesize super-hydrophobic covalent organic polymer powder; carrying out external microcosmic appearance characterization on the super-hydrophobic covalent organic polymer film supported by the copper mesh by adopting SEM; carrying out hydrophobicity test on the super-hydrophobic covalent organic polymer film supported by the copper mesh by adopting a contact angle tester; the self-made oil-water separator is adopted to test the oil-water separation performance of the super-hydrophobic copper mesh/covalent organic polymer composite film.
The specific operation flow of the oil-water separation performance is as follows: the membrane was mounted between clamps, a pre-formulated mixture of various organics and water was poured, free flowing under gravity, and the water trapped by the membrane was poured into an additional beaker and weighed. The oil-water separation performance was evaluated from the separation efficiency η and the flux F of water.
Wherein m is 1 And m 0 The mass of water after and before separation, respectively, V is the volume of oil that permeates the membrane; s is the effective surface area of the membrane and t is the time required for the oil to fully permeate.
The water contact angle of the synthesized superhydrophobic copper mesh/covalent organic polymer composite film is 150.4 degrees, as shown in fig. 4. The super-hydrophobic copper mesh/covalent organic polymer composite film can realize oil-water separation by filtering only by the gravity action of an oil-water mixture at normal temperature and normal pressure, and has the separation effects that: as shown in FIG. 5, the oil and water are completely separated, the water recovery rate is more than 98%, and the flow rate of the permeated oil is higher than 60L/(m) 2 S). As shown in fig. 6, in the circulation experiment of 50 times of oil-water separation, the separation efficiency reaches more than 98%.
The present disclosure is intended to embrace all such alternatives, modifications and variances which fall within the broad scope of the appended claims. Any omissions, modifications, equivalents, improvements, and the like, which are within the spirit and principles of the one or more embodiments of the disclosure, are therefore intended to be included within the scope of the disclosure.
Claims (4)
1. The preparation method of the super-hydrophobic copper mesh/covalent organic polymer composite film is characterized by comprising the following steps of:
preparation of super-hydrophobic copper net/covalent organic polymer composite film
1) Pretreatment of copper mesh
Sequentially ultrasonically cleaning with acetone, ethanol and 1mol/L hydrochloric acid for 10min, removing oil stains on the surface, finally ultrasonically cleaning a solvent on the surface of the copper mesh in deionized water for 10min, and drying for later use;
2) 3-aminopropyl triethoxysilane modification of substrates
Treating the copper mesh dried in step 1) with 3-aminopropyl triethoxysilane at 110 ℃ for 2 hours, washing the copper mesh with ethanol and drying;
3) Trimesic aldehyde modification of substrates
Treating a copper mesh modified by 3-aminopropyl triethoxysilane with trimesic aldehyde at 80 ℃ for 2 hours, and drying for later use;
4) Copper net for synthesizing super-hydrophobic covalent organic polymer film coating by repeated growth method
Preparing trimellitic aldehyde and 4,4' -azobisiniline solutions with the concentration of 0.01mol/L-0.03mol/L respectively by taking dimethyl sulfoxide as a solvent, mixing the two solutions according to the volume ratio, adding 1 mu L of octanoic acid which is not further purified as a catalyst, putting the copper mesh dried in the step 3) into the reaction solution, synthesizing at 120 ℃ for 12 hours, pouring out the solution, adding another fresh synthetic solution with the same concentration into an autoclave for repeated synthesis, repeating the steps for three times to obtain a copper mesh with the final modification time of 36 hours, taking out the copper mesh, washing with acetone and tetrahydrofuran, and drying to obtain the copper mesh loaded with the super-hydrophobic covalent organic polymer film.
2. The super-hydrophobic copper mesh/covalent organic polymer composite film is characterized by being prepared by the preparation method of the super-hydrophobic copper mesh/covalent organic polymer composite film in claim 1.
3. The use of the superhydrophobic copper mesh/covalent organic polymer composite membrane of claim 2 for separation of organic matter and water mixtures.
4. The use according to claim 3, wherein the superhydrophobic copper mesh/covalent organic polymer composite membrane is capable of separating liquid organic matter and water which are mutually insoluble by filtration at normal temperature, and has an oil flux of at least 60L/(m) 2 S) the separation efficiency is still 98% or more in the cycle of 50 times of oil-water separation.
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