CN115536842A - Preparation method of micron tube - Google Patents
Preparation method of micron tube Download PDFInfo
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- CN115536842A CN115536842A CN202211180949.5A CN202211180949A CN115536842A CN 115536842 A CN115536842 A CN 115536842A CN 202211180949 A CN202211180949 A CN 202211180949A CN 115536842 A CN115536842 A CN 115536842A
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0672—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/02—Elements
- C08K3/08—Metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0843—Cobalt
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K2003/0862—Nickel
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Abstract
The application relates to a preparation method of a micron tube in the technical field of micro-nano equipment, which comprises the following steps: selecting a nuclear track membrane; sensitizing and activating the inner wall of the membrane pore of the nuclear pore membrane; flowing a reducing solution containing metal ions for forming the single-metal or alloy microtubes through the pores of the nuclear pore membrane to form a plating layer on the inner walls of the pores of the nuclear pore membrane; and dissolving the nuclear pore membrane to obtain the micron tube. The preparation method of the micron tube is simple to operate, controllable in conditions, efficient, energy-saving, capable of realizing simultaneous reaction of multiple stages of materials, capable of preparing the magnetic micron tube with uniform texture and difficulty in polymerization, and has important application value.
Description
Technical Field
The application relates to the technical field of micro-nano equipment, in particular to a preparation method of a micro-tube.
Background
In recent years, a microtube has attracted much attention due to its superior specific surface area, strong surface activity, etc., for example, a metal microtube is popular because of its good electrical conductivity, mechanical properties and magnetic properties, at present, there are two methods of growth (including prosthetic group catalytic synthesis, self-assembly) and etching (including etching axis and etching mold) for the preparation of the metal microtube, but the metal microtube prepared by growth or etching is easy to have the conditions of non-uniform length, pore diameter and wall thickness, non-uniform tubular bending, non-uniform dispersion, etc., and the phenomena of complicated preparation conditions and difficult control, etc., which greatly affect the use of the microtube.
Disclosure of Invention
The preparation method of the micron tube is simple to operate, controllable in condition, efficient and energy-saving, can realize simultaneous reaction of multi-stage materials, and the prepared micron tube is uniform in texture, highly uniform in pore size, smooth in tube surface and not easy to polymerize.
According to an aspect of the present invention, there is provided a method for preparing a micro-tube, comprising the steps of: selecting a nuclear track membrane; carrying out sensitization treatment and activation treatment on the inner wall of a membrane hole of the nuclear pore membrane; flowing a reducing solution containing metal ions for forming the single-metal or alloy microtubes through the pores of the nuclear pore membrane to form a plating layer on the inner walls of the pores of the nuclear pore membrane; and dissolving the nuclear pore membrane to obtain the micron tube.
By using the preparation method of the micron tube in the technical scheme, the inner wall of the membrane hole of the nuclear pore membrane is sensitized by using a polymer solvent, and the inner wall of the membrane hole of the nuclear pore membrane is activated by using a solvent with a micronucleus effect to form a micronucleus on the inner wall of the membrane hole of the nuclear pore membrane, so that the reduction solution of metal ions is in-situ reduced in the membrane hole, the agglomeration of nano metal particles in the reduction process in the membrane hole is reduced, and the micron tube with uniform texture, uniform pore diameter and smooth surface is finally prepared.
The invention uses dopamine as polymer to be evenly deposited in the membrane pores, which not only can more completely adsorb silver ions, but also can ensure that the surface of the prepared micron tube is smooth and has no collapse; silver nitrate forms Ag micro-cores on the surface of dopamine after being adsorbed by dopamine, which not only can be beneficial to in-situ reduction of a nickel-cobalt reducing solution in membrane pores, but also can reduce agglomeration of nickel-cobalt nano metal particles in the reduction process of the nickel-cobalt nano metal particles in the membrane pores; finally, the micron tube with uniform texture, uniform aperture and smooth surface is prepared.
In addition, the preparation method of the micron tube according to the application can also have the following additional technical characteristics:
in some embodiments of the invention, the pore size of the pores of the nuclear pore membrane is from 0.01 to 30 μm;
preferably, the pore diameter of the pores of the nuclear pore membrane is 0.05-10 μm.
In some embodiments of the present invention, the sensitization of the membrane pores of the nuclear pore membrane comprises the following steps: adding a dopamine polymer into a Tris-HCl buffer solution to prepare a dopamine solution; carrying out ultrasonic stirring on the dopamine solution to obtain a uniformly mixed dopamine solution; flowing a dopamine solution through the pores of the nucleopore membrane; completing the sensitization treatment of the inner wall of the membrane pore of the nuclear pore membrane.
In some embodiments of the invention, the concentration of the dopamine solution is 1.8-2.2g/L.
In some embodiments of the invention, the dopamine solution is ultrasonically stirred for 12 to 36 hours.
In some embodiments of the present invention, sensitization of the pores of the nuclear pore membrane may also use a polymeric solvent such as polypyrrole that can achieve homogeneous deposition and adhesion.
In some embodiments of the present invention, the activating treatment of the membrane pores of the nuclear pore membrane comprises the following steps: adding silver nitrate into deionized water to prepare a silver nitrate solution; flowing a silver nitrate solution through the pores of the nucleopore membrane; the activation treatment of the inner wall of the membrane pores of the nucleopore membrane is completed.
In some embodiments of the invention, the silver nitrate solution has a concentration of 1.2 to 1.8g/L.
In some embodiments of the invention, the silver nitrate is added to deionized water and stirred ultrasonically for 2-7min.
In some embodiments of the present invention, the activation treatment of the membrane pores of the nucleopore membrane can also be performed with a solvent having a micronucleus action.
In some embodiments of the present invention, the reducing solution containing metal ions for forming the single metal or alloy nanotubes comprises nickel sulfate, cobalt sulfate, sodium pyrophosphate, concentrated ammonia water, and dimethylaminoborane and deionized water.
In some embodiments of the present invention, after the nucleopore membrane is dissolved, the silver metal and/or black residue in the dissolving solution is recovered magnetically, and the nanotube is obtained after washing with deionized water for multiple times.
In some embodiments of the present invention, the nucleopore membrane is at least one of polycarbonate, polyester and polyimide, and the solvent used for dissolving the nucleopore membrane is N, N-dimethylacetamide;
preferably, the nuclear pore membrane is made of polycarbonate.
In some embodiments of the invention, the nucleopore membrane is mounted in a filter head, and the dopamine solution, the silver nitrate solution and the reducing solution are all flowed through the pores of the nucleopore membrane using a peristaltic pump filtration method.
Preferably, when the suction filtration solution is a dopamine solution, the rotation speed of a peristaltic pump is 200-600L/min, the suction filtration time is 20-60min, and then air is continuously pumped for 0.5-2min; when the suction filtration solution is silver nitrate solution or reducing solution, the rotation speed of a peristaltic pump is 400-600L/min, the suction filtration time is 10-30min, and then air is continuously pumped for 0.5-2min; wherein, the purpose of continuously pumping air is to dredge the membrane holes.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1. the invention can reduce the deposition of metal on the surface of the membrane by a peristaltic pump filtration method and a filter head, so that the metal is deposited in the membrane hole as much as possible, and in addition, the thickness of the wall of the micron tube is increased along with the extension of the filtration time and the increase of the filtration rotating speed, so that the wall thickness of the micron tube is conveniently adjusted.
2. The invention wraps dopamine on the outer layer of Ni/Co @ PDA micron tube by suction filtration in sequence, and has adsorbability; the magnetic metal is coated on the inner layer of the Ni/Co @ PDA micron tube, so that the Ni/Co @ PDA micron tube has certain stain resistance, and can be used as a special carrier for adsorbing and transporting high molecules such as protein and the like.
3. The nuclear pore membrane made of polycarbonate material has better effects in the aspects of membrane etching sensitivity, pore-forming difficulty, pore diameter control and the like, and is easier to prepare a high-specification micron tube.
Drawings
Various additional advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the application. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
FIG. 1 is a schematic view of the experimental operation flow of multistage preparation of magnetic Ni/Co @ PDA micro-tube based on the modification method of membrane separation technology;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the surface of the nuclear pore membrane and the magnetic Ni/Co @ PDA micro-tube of the present application, FIG. 2a is a SEM image of the surface of the nuclear pore membrane, and FIGS. 2b, 2c and 2d are SEM images of the Ni/Co @ PDA micro-tube at different magnifications, respectively.
Detailed Description
It should be understood that the embodiments described are only a few embodiments of the present application, and not all embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application without making any creative effort belong to the protection scope of the present application.
When the following description refers to the accompanying drawings, like numbers in different drawings represent the same or similar elements unless otherwise indicated. The implementations described in the following exemplary examples do not represent all implementations consistent with the present application. Rather, they are merely examples of apparatus and methods consistent with certain aspects of the application, as detailed in the appended claims.
In the description of the present application, it is to be understood that the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance. The specific meaning of the above terms in the present application can be understood in a specific case by those of ordinary skill in the art. In addition, in the description of the present application, "a plurality" means two or more unless otherwise specified. "and/or" describes the association relationship of the associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a exists alone, A and B exist simultaneously, and B exists alone. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In order to facilitate understanding of the preparation method of the microtube provided in the embodiment of the present application, an application scenario of the preparation method is first described, and the preparation method of the microtube provided in the embodiment of the present application is used for preparing the microtube; in recent years, microtubes have attracted much attention because of their excellent large specific surface area, strong surface activity, etc., and among them, metal microtubes are popular because of their good electrical conductivity, mechanical properties, and magnetic properties; at present, two methods of growth and etching are mainly used for preparing the metal micron tube, and the prepared metal micron tube has the phenomena of non-uniform length, aperture and wall thickness, tubular bending, non-uniform dispersion, complex preparation conditions, difficult control and the like, and the research and development of the metal micron tube are greatly limited.
Wherein, nickel and cobalt metal play an important role in the fields of hydrogen storage materials, catalytic degradation, super capacitors and the like because of good hydrogen evolution and storage performance and catalytic activity; compared with the traditional material, the nickel and cobalt tubular material has larger specific surface area and can better show excellent performance; in recent years, nickel and cobalt metals are developed into metal microtubes, but the prepared microtubes still have the problems of different tube hole diameters, unsmooth tube surfaces and easiness in polymerization.
Therefore, the preparation method of the micron tube is simple to operate, controllable in conditions, efficient and energy-saving, capable of achieving simultaneous reaction of multiple materials, capable of preparing the magnetic micron tube with uniform texture and low possibility of polymerization, and has important application value.
The nuclear pore membrane related to the application has universality, the shape of straight pores formed by the membrane pores can be used as a template for preparation, the nuclear pore membranes such as a common polycarbonate membrane (PC), a polyester membrane (PET), a polyimide membrane (PI) and the like can be used as the template for preparation, the use effect of the nuclear pore membrane made of the polycarbonate material is optimal in consideration of the advantages of membrane etching sensitivity, cheap pore forming, controllable pore diameter and the like, the pore diameter range of the membrane pores of the nuclear pore membrane can be 0.01-30 mu m, the pore diameter of the further membrane pores can be 0.05-10 mu m, and the nuclear pore membrane with the pore diameter of 0.2 mu m is used for description in each embodiment of the application.
In the application, when the prepared single metal or alloy micron tube is a non-magnetic single metal or alloy micron tube, the magnetic recovery micron tube can be used for cleaning, and when the micron tube is a non-magnetic single metal or alloy micron tube, the separation can be performed in a centrifugal or suction filtration mode, and then the cleaning is performed.
The preparation method of the microtube provided by the embodiment of the application is explained by taking the magnetic Ni/Co @ PDA microtube as an example with the accompanying drawing; FIG. 1 is a schematic diagram of an experimental operation flow of the multistage preparation of a magnetic Ni/Co @ PDA micro-tube based on a membrane separation technology modification method; FIG. 2 is a scanning electron microscope image of the surface of the nuclear pore membrane and the magnetic Ni/Co @ PDA micro-tube of the present application, wherein FIG. 2a is a scanning electron microscope image of the surface of the nuclear pore membrane, and FIGS. 2b, 2c and 2d are scanning electron microscope images of the Ni/Co @ PDA micro-tube at different magnifications, respectively.
Example 1
S1, preparing a dopamine solution; adding 2.422g of Tirs into a clean beaker, then adding 200mL of deionized water, uniformly stirring, adjusting the pH value to 8.5 by using 0.1M HCl solution, then adding 0.4g of PDA (dopamine), and performing ultrasonic treatment and stirring for 24 hours to obtain a dopamine solution with the uniformly mixed concentration of 2g/L for later use.
S2, installing a nuclear track membrane; fixing a clean nuclear pore membrane made of polycarbonate with the pore diameter of 0.2 mu m in a detachable filter head with the diameter of 25mm, screwing the filter heads to ensure the sealing property, connecting a plurality of filter heads in front and back, connecting the beginning and the end of the two outermost filter heads by two hoses, and enabling one hose to pass through a peristaltic pump for standby.
And S3, placing the remaining two ends of the two hoses in the step S2 into the dopamine solution in the step S1, opening a peristaltic pump to adjust the rotating speed to 400L/min, performing suction filtration at room temperature for 30min in a circulating mode, removing the dopamine solution to enable the dopamine to be uniformly deposited in the membrane pores, and then continuing pumping air for 1min to discharge the remaining dopamine solution in the hoses and dredging the membrane pores.
And S4, adding 0.3194g of silver nitrate into 200mL of deionized water, ultrasonically stirring for 5min to prepare a silver nitrate solution with the concentration of 1.597g/L, repeating the peristaltic pump suction filtration process in the step S3, wherein the rotating speed of the peristaltic pump is 500L/min, the circulating suction filtration time is 20min, continuously pumping air for 1min, pumping the silver nitrate solution, and adsorbing silver ions by dopamine deposited in membrane pores in the step S3 to perform in-situ reduction to form Ag micronuclei.
S5, adding 12.5g of nickel sulfate, 12.5g of cobalt sulfate, 50g of sodium pyrophosphate, 45ml of 28% concentrated ammonia water and 1.5g of dimethylaminoborane into 1L of deionized water in sequence, ultrasonically stirring for 15min to prepare a reducing solution containing nickel sulfate and cobalt sulfate, repeating the peristaltic pump suction filtration process in the step S3, wherein the rotation speed of a peristaltic pump is 500L/min, the circulating suction filtration time is 20min, the air is continuously pumped for 1min, the nickel-cobalt reducing solution is pumped, the Ag micro-core in the step S4 promotes the nickel-cobalt reducing solution to carry out in-situ reduction in the membrane pores, and reduces the agglomeration of nickel-cobalt nano metal particles in the reduction process in the membrane pores, so that the nuclear pore membrane is coated with nickel and cobalt metals to form a metal layer.
S6, after the reaction is finished, the filter head is detached, the surface of the membrane is washed for 3 times by deionized water, then the excessive moisture is absorbed, and the membrane is placed in a clean beaker for standby.
S7, adding a certain amount of N, N-dimethylacetamide into the beaker, obtaining a micron tube after the membrane structure is melted, dispersing the micron tube, performing ultrasonic treatment for 20min to further improve the effect, wherein when the reaction is incomplete or just completed, nano metal particles deposited on the inner wall of the Ni/Co @ PDA micron tube are deposited to be black, and when the reaction is completed, the nano metal particles deposited on the inner wall of the Ni/Co @ PDA micron tube are agglomerated to expose metal luster; then, silver metal and/or black residue in the solution is recovered by magnetism, and the solution is washed for 3 times by deionized water to obtain the Ni/Co @ PDA micro-tube.
Example 2
S1, preparing a dopamine solution; adding 2.422g of Tirs into a clean beaker, then adding 200mL of deionized water, uniformly stirring, adjusting the pH value to 8.5 by using 0.1M HCl solution, then adding 0.36g of dopamine polymer into the solution, performing ultrasonic treatment and stirring for 12 hours to obtain a dopamine solution with uniform mixing concentration of 1.8g/L for later use.
S2, installing a nuclear track membrane; fixing a clean nuclear pore membrane made of polycarbonate with the pore diameter of 0.2 mu m in a detachable filter head with the diameter of 25mm, screwing the filter heads to ensure the sealing property, connecting a plurality of filter heads in front and back, connecting the beginning and the end of the two outermost filter heads by two hoses, and enabling one hose to pass through a peristaltic pump for standby.
And S3, placing the remaining two ends of the two hoses in the step S2 into the dopamine solution in the step S1, turning on a peristaltic pump to adjust the rotating speed to 200L/min, performing circulating suction filtration at room temperature for 20min, removing the hoses to enable dopamine to be uniformly deposited in the membrane holes, and then continuously pumping air for 1min to discharge the remaining dopamine solution in the hoses and dredge the membrane holes.
And S4, adding 0.24g of silver nitrate into 200mL of deionized water, ultrasonically stirring for 2min to prepare a silver nitrate solution with the concentration of 1.2g/L, repeating the peristaltic pump suction filtration process in the step S3, wherein the rotating speed of the peristaltic pump is 400L/min, the circulating suction filtration time is 10min, continuing pumping air for 1min, pumping the silver nitrate solution, and adsorbing silver ions by dopamine deposited in membrane pores in the step S3 to perform in-situ reduction to form Ag micronuclei.
S5, adding 12.5g of nickel sulfate, 12.5g of cobalt sulfate, 50g of sodium pyrophosphate, 45ml of 28% concentrated ammonia water and 1.5g of dimethylaminoborane into 1L of deionized water in sequence, ultrasonically stirring for 10min to prepare a reducing solution containing nickel sulfate and cobalt sulfate, repeating the suction filtration process of the peristaltic pump in the step S3, wherein the rotation speed of the peristaltic pump is 400L/min, the circulating suction filtration time is 10min, the air is continuously pumped for 1min, the reducing solution of nickel and cobalt is pumped, the Ag micro-core in the step S4 promotes the reducing solution of nickel and cobalt to carry out in-situ reduction in the membrane pores, and reduces the agglomeration of nickel and cobalt nano-metal particles in the reduction process in the membrane pores, so that the nuclear pore membrane is coated with nickel and cobalt metals to form a metal layer.
S6, after the reaction is finished, the filter head is detached, the surface of the membrane is washed for 3 times by deionized water, then the excessive moisture is absorbed, and the membrane is placed in a clean beaker for standby.
S7, adding a certain amount of N, N-dimethylacetamide into the beaker, obtaining a micron tube after the membrane structure is melted, dispersing the micron tube, performing ultrasonic treatment for 20min to further improve the effect, wherein when the reaction is incomplete or just completed, nano metal particles deposited on the inner wall of the Ni/Co @ PDA micron tube are deposited to be black, and when the reaction is completed, the nano metal particles deposited on the inner wall of the Ni/Co @ PDA micron tube are agglomerated to expose metal luster; then, the silver metal and/or black residue in the solution is recovered by magnetism, and the Ni/Co @ PDA micro-tube is obtained after 3 times of washing by deionized water.
Example 3
S1, preparing a dopamine solution; adding 2.422g of Tirs into a clean beaker, then adding 200mL of deionized water, uniformly stirring, adjusting the pH value to 8.5 by using 0.1M HCl solution, then adding 0.44g of dopamine polymer into the solution, performing ultrasonic treatment, and stirring for 36 hours to obtain a dopamine solution with uniform mixing concentration of 2.2g/L for later use.
S2, installing a nuclear track membrane; fixing a clean nuclear pore membrane made of polycarbonate with the pore diameter of 0.2 mu m in a detachable filter head with the diameter of 25mm, screwing the filter heads to ensure the sealing property, connecting a plurality of filter heads in front and back, connecting the beginning and the end of the two outermost filter heads by two hoses, and enabling one hose to pass through a peristaltic pump for standby.
And S3, placing the remaining two ends of the two hoses in the step S2 into the dopamine solution in the step S1, opening a peristaltic pump to adjust the rotating speed to 600L/min, performing suction filtration at room temperature for 60min, removing the dopamine solution to enable the dopamine to be uniformly deposited in the membrane pores, and then continuing pumping air for 1min to discharge the remaining dopamine solution in the hoses and dredging the membrane pores.
And S4, adding 0.36g of silver nitrate into 200mL of deionized water, ultrasonically stirring for 7min to prepare a silver nitrate solution with the concentration of 1.8g/L, repeating the peristaltic pump suction filtration process in the step S3, wherein the rotating speed of the peristaltic pump is 600L/min, the circulating suction filtration time is 30min, continuing pumping air for 1min, pumping the silver nitrate solution, and carrying out in-situ reduction on the dopamine deposited in the membrane pores in the step S3 to form Ag micronuclei.
S5, adding 12.5g of nickel sulfate, 12.5g of cobalt sulfate, 50g of sodium pyrophosphate, 45ml of 28% concentrated ammonia water and 1.5g of dimethylaminoborane into 1L of deionized water in sequence, ultrasonically stirring for 20min to prepare a reducing solution containing nickel sulfate and cobalt sulfate, repeating the peristaltic pump suction filtration process in the step S3, wherein the rotation speed of a peristaltic pump is 600L/min, the circulating suction filtration time is 30min, the air is continuously pumped for 1min, the nickel-cobalt reducing solution is pumped, the Ag micro-core in the step S4 promotes the nickel-cobalt reducing solution to carry out in-situ reduction in the membrane pores, and reduces the agglomeration of nickel-cobalt nano metal particles in the reduction process in the membrane pores, so that the nuclear pore membrane is coated with nickel and cobalt metals to form a metal layer.
S6, after the reaction is finished, the filter head is detached, the surface of the membrane is washed for 3 times by deionized water, then the excessive moisture is absorbed, and the membrane is placed in a clean beaker for standby.
S7, adding a certain amount of N, N-dimethylacetamide into the beaker, obtaining a micron tube after the membrane structure is melted, dispersing the micron tube, performing ultrasonic treatment for 20min to further improve the effect, wherein when the reaction is incomplete or just completed, nano metal particles deposited on the inner wall of the Ni/Co @ PDA micron tube are deposited to be black, and when the reaction is completed, the nano metal particles deposited on the inner wall of the Ni/Co @ PDA micron tube are agglomerated to expose metal luster; then, the silver metal and/or black residue in the solution is recovered by magnetism, and the Ni/Co @ PDA micro-tube is obtained after 3 times of washing by deionized water.
SEM test was conducted on the nuclear pore membrane of example 1 and the obtained Ni/Co @ PDA microtube; FIG. 2 is a scanning electron microscope image of the surface of the nuclear pore membrane and the magnetic Ni/Co @ PDA micro-tube, FIG. 2a is a scanning electron microscope image of the surface of the nuclear pore membrane, and FIGS. 2b, 2c and 2d are scanning electron microscope images of the Ni/Co @ PDA micro-tube at different magnifications, respectively.
According to the results, as shown in fig. 2a and 2b, the prepared tubular material has the same pore diameter and length as those of the nuclear pore membrane, and as shown in fig. 2c and 2d, the grain structure of the surface of the prepared tubular material proves that the Ni/Co metal is successfully coated on the carrier. The invention uses dopamine as polymer to be evenly deposited in the membrane pores, which not only can more completely adsorb silver ions, but also can ensure that the surface of the prepared micron tube is smooth and has no collapse; silver nitrate can form Ag micro-cores on the surface of dopamine after being adsorbed by the dopamine, so that the in-situ reduction of a nickel-cobalt reducing solution in a membrane pore can be facilitated, and the agglomeration of nickel-cobalt nano metal particles in the reduction process of the nickel-cobalt nano metal particles in the membrane pore can be reduced; finally, the micron tube with uniform texture, uniform aperture and smooth surface is prepared.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The preparation method of the micron tube is characterized by comprising the following steps:
selecting a nuclear track membrane;
carrying out sensitization treatment and activation treatment on the inner wall of a membrane hole of the nuclear pore membrane;
flowing a reducing solution containing metal ions for forming the single-metal or alloy microtubes through the pores of the nuclear pore membrane to form a plating layer on the inner walls of the pores of the nuclear pore membrane;
and dissolving the nuclear pore membrane to obtain the micron tube.
2. The method of claim 1, wherein the pore diameter of the pore of the nuclear pore membrane is 0.05 to 10 μm.
3. The method for preparing the microtube according to claim 1, wherein the sensitization of the pores of the nuclear pore membrane comprises the steps of:
adding a dopamine polymer into a Tris-HCl buffer solution to prepare a dopamine solution;
carrying out ultrasonic stirring on the dopamine solution to obtain a uniformly mixed dopamine solution;
flowing a dopamine solution through the pores of the nucleopore membrane;
completing the sensitization treatment of the inner wall of the membrane pore of the nuclear pore membrane.
4. The method for preparing the microtube according to claim 3, wherein the concentration of the dopamine solution is 1.8-2.2g/L.
5. The preparation method of the microtube according to claim 3, wherein the time of the ultrasonic agitation of the dopamine solution is 12-36h.
6. The method for preparing the microtube according to claim 1, wherein the activation treatment of the pore of the nucleopore membrane comprises the steps of:
adding silver nitrate into deionized water to prepare a silver nitrate solution;
flowing silver nitrate solution through the pores of the nucleopore membrane;
the activation treatment of the inner wall of the membrane pores of the nucleopore membrane is completed.
7. The method for preparing the microtube according to claim 6, wherein the concentration of the silver nitrate solution is 1.2-1.8g/L.
8. The method of claim 1, wherein the reducing solution containing metal ions for forming the single metal or alloy nanotubes comprises nickel sulfate, cobalt sulfate, sodium pyrophosphate, concentrated ammonia, dimethyl amino borane, and deionized water.
9. The method of claim 8, wherein after the nanopore membrane is dissolved, silver metal and/or black residues in the solution are magnetically recovered, and the nanotube is obtained after washing with deionized water for a plurality of times.
10. The method for preparing the microtube according to claim 1, wherein the nucleopore membrane is at least one of polycarbonate, polyester and polyimide, and the solvent used for dissolving the nucleopore membrane is N, N-dimethylacetamide;
preferably, the nuclear pore membrane is made of polycarbonate.
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| CN102719824A (en) * | 2012-06-12 | 2012-10-10 | 天津大学 | Dopamine-nanosilver composite coating and preparation method thereof |
| CN103418250A (en) * | 2013-07-05 | 2013-12-04 | 烟台绿水赋膜材料有限公司 | Method of in-situ generation of nano particle on separating membrane surface |
| US20140336040A1 (en) * | 2012-01-05 | 2014-11-13 | Nanyang Technological University | Methods of preparing monodispersed polydopamine nano- or microspheres, and methods of preparing nano- or microstructures based on the polydopamine nano- or microspheres |
| US20170203256A1 (en) * | 2016-01-19 | 2017-07-20 | Uchicago Argonne, Llc | Magnetic nanotube composite membranes |
| CN115282784A (en) * | 2022-01-21 | 2022-11-04 | 浙江师范大学 | Modified magnetic nickel/cobalt @ polydopamine microtube and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140336040A1 (en) * | 2012-01-05 | 2014-11-13 | Nanyang Technological University | Methods of preparing monodispersed polydopamine nano- or microspheres, and methods of preparing nano- or microstructures based on the polydopamine nano- or microspheres |
| CN102719824A (en) * | 2012-06-12 | 2012-10-10 | 天津大学 | Dopamine-nanosilver composite coating and preparation method thereof |
| CN103418250A (en) * | 2013-07-05 | 2013-12-04 | 烟台绿水赋膜材料有限公司 | Method of in-situ generation of nano particle on separating membrane surface |
| US20170203256A1 (en) * | 2016-01-19 | 2017-07-20 | Uchicago Argonne, Llc | Magnetic nanotube composite membranes |
| CN115282784A (en) * | 2022-01-21 | 2022-11-04 | 浙江师范大学 | Modified magnetic nickel/cobalt @ polydopamine microtube and preparation method thereof |
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