CN110180218B - Microphone-shaped MOFs-based oil-water separation metal net film and preparation method thereof - Google Patents
Microphone-shaped MOFs-based oil-water separation metal net film and preparation method thereof Download PDFInfo
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- CN110180218B CN110180218B CN201910494599.1A CN201910494599A CN110180218B CN 110180218 B CN110180218 B CN 110180218B CN 201910494599 A CN201910494599 A CN 201910494599A CN 110180218 B CN110180218 B CN 110180218B
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Abstract
The invention providesA microphone-shaped MOFs-based oil-water separation metal net film and a preparation method thereof, wherein the metal net film comprises a copper net and Cu (OH) growing on the surface of the copper net in situ2And with Cu (OH)2Cu-CAT-1 (one of MOFs) grown as a template. The cylindrical MOFs-based oil-water separation metal mesh membrane is prepared by a hydrothermal method and the like. The metal net film has excellent super-hydrophilic/underwater super-oleophobic property and super-strong oil stain resistance, shows excellent separation effect on different kinds of oil/water mixtures, and has huge application prospect and reference value in the aspect of oil/water mixture separation.
Description
Technical Field
The invention relates to a microphone-shaped MOFs-based oil-water separation metal net film and a preparation method thereof, belonging to the technical field of new materials.
Background
The frequent occurrence of oil leakage accidents and the discharge of oily sewage in life cause serious environmental pollution and resource waste, and how to efficiently treat the oily sewage is a difficult problem for people at present. Many traditional methods such as ultrasonic, centrifugal, air flotation and chemical methods are commonly used for separating oil/water mixture, but are limited by the disadvantages of complex process, high cost, low efficiency and easy generation of secondary pollution. In recent years, membrane separation technology based on a special wettability surface has attracted much attention due to its advantages of high separation performance, low energy consumption, convenient operation, greenness, no pollution, and the like.
The surface wettability has great influence on the oil-water separation performance of the membrane material, so researchers can adjust the surface wettability of the membrane as required to adjust the oil-water separation performance of the membrane material, and the main means comprises adjusting the surface components of the membrane and constructing a surface micro-nano multi-level structure. Metal organic framework compounds (MOFs) are used as a new porous crystal material, and are increasingly applied to the field of oil-water separation due to the advantages of high specific surface area, high porosity, regular pore channels and the likeTo focus on. For example, Zhang et al successfully designed and prepared a metallic mesh film based on UIO-66 (a kind of MOFs) coating by a simple solution immersion process, and found that the film has super-hydrophilicity and super-lipophobicity under water, and exhibits super-high water flux and excellent separation efficiency in the oil-water separation process (ACS appl. Mater. interfaces 2018,10, 17301-17308); plum et al, which uses a stainless steel wire mesh (SSM) as a base material, modifies aminated UiO-66 and Graphene Oxide (GO) onto the surface of the SSM by a simple self-assembly method, and constructs SSM/UiO-66-NH2a/GO multi-stage structure exhibiting super-hydrophilicity, superior oil stain resistance, and a remarkable oil-water separation effect (j. hazard. mater.2019,373, 725-732). The application of Cu-CAT-1 as an MOFs material with super-hydrophilicity and super-oleophobicity under water in the field of membrane separation of oil/water mixtures is rarely reported.
The invention selects a copper net with excellent mechanical property and corrosion resistance as a carrier, firstly, copper hydroxide (Cu (OH) grows in situ2) The nanowire array is used as a sacrificial template, a copper source for later-stage growth of Cu-CAT-1 is provided, and then Cu/Cu (OH) with a microphone-shaped micro-nano rough structure on the surface is constructed by a simple hydrothermal method2the/Cu-CAT-1 multilevel structure. The metal net film has excellent super-hydrophilic/underwater super-oleophobic property and super-strong oil stain resistance, shows excellent separation effect on different oil-water mixtures, and has huge application prospect and reference value in the aspect of oil/water mixture separation.
Disclosure of Invention
The invention aims to provide a microphone-shaped MOFs-based oil-water separation metal net film and a preparation method thereof, and can solve the problems of low flux, easy pollution and the like of the conventional oil-water separation film.
The technical problem to be solved by the invention for achieving the purpose is to prepare the tubular MOFs-based metal mesh membrane by a hydrothermal method and other methods so as to obtain an oil-water separation membrane with excellent performance.
In order to achieve the above objects, in one aspect, the present specification provides a microphone-shaped MOFs-based oil-water separation metal mesh film, which is characterized by comprising a copper mesh, and cu (oh) grown in situ on the surface of the copper mesh2And with Cu (OH)2Cu-CAT-1 (one of MOFs) grown as a template, the aperture of a copper mesh is 32-45 mu m, and Cu (OH)2The length is 8-15 mu m, the diameter is 220-580 nm, the length of Cu-CAT-1 is 7-13 mu m, and the diameter of the tip microsphere of Cu-CAT-1 is 0.8-2 mu m.
In the above cylindrical MOFs-based oil-water separation metal mesh film, the mesh number of the copper mesh is preferably 400 mesh.
In the cylindrical MOFs-based oil-water separation metal mesh film, the surface of the pointed microsphere of Cu-CAT-1 preferably has micro-nano protrusions with the size of tens of nanometers.
In another aspect, the present specification provides a method for producing the cylindrical MOFs-based oil-water separation metal mesh film, comprising the steps of:
(1) cutting a 400-mesh copper net into squares with the side length of 5 cm, sequentially putting the squares in acetone, ethanol and deionized water, performing ultrasonic treatment for 30 minutes respectively, and performing vacuum drying at 25 ℃;
(2) preparing a first solution, wherein sodium hydroxide and ammonium persulfate are dissolved in the first solution, a solvent is water, and the mass ratio of the sodium hydroxide to the ammonium persulfate is 3.37: 1.00;
(3) immersing the copper mesh obtained in the step (1) into the first solution, reacting for 30 minutes at room temperature, taking out, repeatedly washing a product with deionized water, and drying at room temperature;
(4) preparing a second solution, wherein the second solution is prepared by dissolving 35 mg of 2, 3, 6, 7, 10, 11-hexahydroxy triphenylene in water and N, N-dimethylformamide in a volume ratio of 10: 1;
(5) and (4) immersing the product obtained in the step (3) into the solution II, reacting for 45 minutes at room temperature, taking out, washing with acetone and deionized water, and drying in vacuum at room temperature to complete the preparation of the microphone-shaped MOFs-based oil-water separation metal net film.
The microphone-shaped MOFs-based oil-water separation metal net film can be applied to the aspect of preparing oil-water separation membranes, technical means for separating oil/water mixtures are expanded, the microphone-shaped MOFs-based oil-water separation metal net film has high separation flux and separation efficiency for different types of oil/water mixtures, and the microphone-shaped MOFs-based oil-water separation metal net film is strong in oil stain resistance, easy to clean, good in recycling performance and has huge application prospects and reference values in the aspect of separating oil/water mixtures.
Description of the drawings:
fig. 1 is a Scanning Electron Microscope (SEM) image of a microphone-shaped MOFs-based oil-water separation metal mesh film prepared in the examples of the present specification, wherein the left half of fig. 1 is an SEM image of the surface of the metal mesh film under low magnification, the right half of fig. 1 is an SEM image of the surface of the metal mesh film under high magnification, and the right half of fig. 1 is an SEM image of the microstructure of the surface of the tip microsphere of the MOFs (Cu-CAT-1) in the inset.
Fig. 2 is a schematic diagram of the separation of oil/water mixture from a microphone-shaped MOFs-based oil-water separation metal net prepared in the examples of the present specification, wherein the left half of fig. 2 is a diagram of pouring the oil-water mixture into the upper half of the container during the separation, and the right half of fig. 2 is a diagram of the effect after the separation.
The specific implementation mode is as follows:
the present invention is described in detail below with reference to the drawings and examples.
Example 1
The embodiment specifically prepares a microphone-shaped MOFs-based oil-water separation metal net film, and the preparation process is as follows:
(1) cutting a 400-mesh copper net into squares with the side length of 5 cm, sequentially putting the squares in acetone, ethanol and deionized water, performing ultrasonic treatment for 30 minutes respectively, and performing vacuum drying at 25 ℃ to obtain a clean copper net;
(2) firstly, adding 10 g of sodium hydroxide into 100 ml of deionized water, carrying out magnetic stirring, adding 2.9666 g of ammonium persulfate after the sodium hydroxide is completely dissolved, and carrying out magnetic stirring on the solution to obtain a clear and transparent solution I;
(3) immersing the clean copper mesh obtained in the step (1) into the first solution, reacting for 30 minutes at room temperature, taking out, repeatedly washing the product with deionized water, and drying at room temperature to obtain Cu (OH)2Growth on a copper grid to give Cu/Cu (OH)2；
(4) Weighing 35 mg of 2, 3, 6, 7, 10, 11-hexahydroxy triphenylene, adding the weighed materials into a mixed solution of 50 ml of water and 5 ml of N, N-dimethylformamide, carrying out magnetic stirring for 20 minutes, then carrying out ultrasonic treatment for 10 minutes, and carrying out magnetic stirring for 20 minutes to obtain a solution II;
(5) and (4) immersing the product obtained in the step (3) into the solution II, reacting for 45 minutes at room temperature, taking out, washing with acetone and deionized water, and drying in vacuum at room temperature to complete the preparation of the microphone-shaped MOFs-based oil-water separation metal net film.
FIG. 1 shows an SEM image of a microphone-shaped MOFs-based oil-water separation metal net film, and from the SEM image, a micro-nano multilevel structure of a cylindrical Cu-CAT-1 on a copper net can be clearly seen, wherein the length of the Cu-CAT-1 is 7-13 μm, and the diameter of a tip microsphere of the Cu-CAT-1 is 0.8-2 μm.
Fig. 2 shows a schematic diagram of a specific oil/water mixture separation process for a microphone-like MOFs-based oil-water separation metal mesh, from which it is evident that the oil/water mixture is initially poured into the upper half of the vessel, after which the water in the oil/water mixture will pass through the metal mesh under the influence of gravity into the lower half of the vessel, while the oil is trapped in the upper half of the vessel.
Claims (3)
1. A microphone-shaped MOFs-based oil-water separation metal net film is characterized in that: the metal net film comprises a copper net, Cu (OH) growing on the surface of the copper net in situ2And with Cu (OH)2Cu-CAT-1 is grown as a template, the aperture of a copper mesh is 32-45 mu m, and Cu (OH)2The length is 8-15 mu m, the diameter is 220-580 nm, the length of Cu-CAT-1 is 7-13 mu m, the diameter of the tip microsphere of Cu-CAT-1 is 0.8-2 mu m, and the surface of the microsphere is also provided with a nano-scale protrusion structure.
2. The microphone-shaped MOFs-based oil-water separation metal mesh film according to claim 1, wherein the Cu-CAT-1 nanorods are shaped like a microphone.
3. A preparation method of a microphone-shaped MOFs-based oil-water separation metal net film is characterized by comprising the following steps:
(1) cutting a 400-mesh copper net into squares with the side length of 5 cm, sequentially putting the squares in acetone, ethanol and deionized water, performing ultrasonic treatment for 30 minutes respectively, and performing vacuum drying at 25 ℃;
(2) preparing a first solution, wherein sodium hydroxide and ammonium persulfate are dissolved in the first solution, a solvent is water, and the mass ratio of the sodium hydroxide to the ammonium persulfate is 3.37: 1.00;
(3) immersing the copper mesh obtained in the step (1) into the first solution, reacting for 30 minutes at room temperature, taking out, repeatedly washing a product with deionized water, and drying at room temperature;
(4) preparing a second solution, wherein the second solution is prepared by dissolving 35 mg of 2, 3, 6, 7, 10, 11-hexahydroxy triphenylene in water and N, N-dimethylformamide in a volume ratio of 10: 1;
(5) and (4) immersing the product obtained in the step (3) into the solution II, reacting for 45 minutes at room temperature, taking out, washing with acetone and deionized water, and drying in vacuum at room temperature to complete the preparation of the microphone-shaped MOFs-based oil-water separation metal net film.
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| CN111146014A (en) * | 2020-01-10 | 2020-05-12 | 华东师范大学 | Cu @ Cu-CAT @ PANI composite electrode material, and preparation method and application thereof |
| CN111543436B (en) * | 2020-04-21 | 2021-04-02 | 北京科技大学 | Efficient antibacterial and antivirus copper-based filter screen with hierarchical structure and preparation method |
| CN112851960B (en) * | 2021-01-20 | 2022-12-23 | 江苏理工学院 | Super-hydrophobic metal organic framework material and preparation method and application thereof |
| CN115364698B (en) * | 2022-05-19 | 2023-08-04 | 同济大学 | Organic metal frame loaded copper mesh surface separation membrane and preparation method and application thereof |
| CN115634660A (en) * | 2022-09-09 | 2023-01-24 | 理工清科(重庆)先进材料研究院有限公司 | Photo-thermal driving air water-collecting composite material, and preparation method and application thereof |
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