CN113584723A - Liquid metal nanoparticle composite nanofiber membrane and preparation method and application thereof - Google Patents
Liquid metal nanoparticle composite nanofiber membrane and preparation method and application thereof Download PDFInfo
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
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- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
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- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4282—Addition polymers
- D04H1/4309—Polyvinyl alcohol
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- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4282—Addition polymers
- D04H1/4318—Fluorine series
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- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
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Abstract
The invention provides a liquid metal nanoparticle composite nanofiber membrane as well as a preparation method and application thereof, belonging to the technical field of electrostatic spinning and comprising the following steps: separately providing a suspension of liquid metal nanoparticles and an aqueous solution of a polymer; and mixing the suspension of the liquid metal nano particles with an aqueous solution of a polymer, and carrying out electrostatic spinning to obtain the liquid metal nano particle composite nanofiber membrane. According to the invention, the aqueous solution of the polymer is used as the electrostatic spinning solution, the liquid metal nanoparticles are added into the electrostatic spinning solution, and the liquid metal nanoparticles are loaded on the surface of the nanofiber or embedded in the nanofiber through electrostatic spinning to form the composite nanofiber membrane with the self-supporting three-dimensional porous structure.
Description
Technical Field
The invention relates to the technical field of electrostatic spinning, in particular to a liquid metal nanoparticle composite nanofiber membrane and a preparation method and application thereof.
Background
The organic/metal composite nanofiber has good electric conduction and electric heating performance of metal, has good mechanical property of nanofiber, and has wide application in various fields.
At present, the preparation methods of the organic/metal composite nanofiber mainly comprise an in-situ polymerization method and a sol-gel method. The in-situ polymerization method is a method for dispersing metal nanoparticles in a monomer and polymerizing the monomer into a high polymer by initiating a polymerization reaction, so that the metal nanoparticles and the nanofibers are polymerized in situ, but the method easily causes the nanoparticles to be aggregated in the polymer and cannot be uniformly dispersed; the sol-gel method generally uses a metal organic compound as a precursor, forms a sol through hydrolysis and polymerization under certain conditions, and converts the sol into a gel through processes such as solvent volatilization or heating to form a composite material, but the method requires multiple reactions and is complex in process.
Therefore, how to simplify the preparation process and make the metal nanoparticles dispersed in the nanofibers more uniformly is a problem in the prior art.
Disclosure of Invention
The invention aims to provide a liquid metal nanoparticle composite nanofiber membrane as well as a preparation method and application thereof. The preparation method provided by the invention has simple process, and the metal nano particles can be uniformly loaded on the surface of the nano fiber or embedded in the nano fiber.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a liquid metal nanoparticle composite nanofiber membrane, which comprises the following steps:
(1) separately providing a suspension of liquid metal nanoparticles and an aqueous solution of a polymer;
(2) and (2) mixing the suspension of the liquid metal nano particles obtained in the step (1) with an aqueous solution of a polymer, and carrying out electrostatic spinning to obtain the liquid metal nano particle composite nanofiber membrane.
Preferably, the liquid metal nanoparticles in step (1) are made of gallium indium tin alloy or gallium indium alloy.
Preferably, the method for preparing the suspension of liquid metal nanoparticles in step (1) comprises: mixing the liquid metal with a solvent and a stabilizer, and carrying out stirring and/or ultrasonic treatment to obtain a suspension of liquid metal nanoparticles.
Preferably, the stabilizer comprises polyvinylpyrrolidone, polyoxyethylene polyoxypropylene ether F127, dodecanethiol, sodium dodecylbenzenesulfonate or N, N-dimethylacetamide; the mass ratio of the stabilizer to the liquid metal is (1-2): 1.
preferably, the volume ratio of the mass of the liquid metal to the solvent is 1g (15-25) mL.
Preferably, the polymer in step (1) comprises polyvinyl alcohol, polyethylene oxide, polyimide or polyvinylidene fluoride; the mass concentration of the aqueous solution of the polymer is 5-15%.
Preferably, the mass ratio of the liquid metal nanoparticles to the polymer in the step (2) is 1 (1-3).
Preferably, the spinning voltage of the electrostatic spinning in the step (2) is 7-15 kV, the receiving distance is 8-15 cm, and the advancing speed is 0.1-0.5 mm/min.
The invention provides the liquid metal nanoparticle composite nanofiber membrane prepared by the preparation method in the technical scheme.
The invention also provides application of the liquid metal nanoparticle composite nanofiber membrane in Raman detection.
The invention provides a preparation method of a liquid metal nanoparticle composite nanofiber membrane, which comprises the following steps: separately providing a suspension of liquid metal nanoparticles and an aqueous solution of a polymer; and mixing the suspension of the liquid metal nano particles with an aqueous solution of a polymer, and carrying out electrostatic spinning to obtain the liquid metal nano particle composite nanofiber membrane. The invention adopts the aqueous solution of the polymer as the electrostatic spinning solution, adds the liquid metal nano-particles into the electrostatic spinning solution, and loads the liquid metal nano-particles on the surface of the nano-fibers or embeds the liquid metal nano-particles into the nano-fibers through electrostatic spinning to form the composite nano-fiber film with the self-supporting three-dimensional porous structure.
Drawings
Fig. 1 is a flow chart of a process for preparing a liquid metal nanoparticle composite nanofiber membrane according to example 1 of the present invention;
fig. 2 is an SEM image of a liquid metal nanoparticle composite nanofiber membrane prepared in example 1 of the present invention;
FIG. 3 is SEM images of different parts of a liquid metal nanoparticle composite nanofiber membrane prepared in example 1 of the present invention;
FIG. 4 is an SEM image of a liquid metal nanoparticle composite nanofiber membrane prepared in example 1 of the present invention at a small magnification;
fig. 5 is an EDS diagram of a liquid metal nanoparticle composite nanofiber membrane prepared in example 1 of the present invention;
fig. 6 is an SEM image of a liquid metal nanoparticle composite nanofiber membrane prepared in example 2 of the present invention.
Detailed Description
The invention provides a preparation method of a liquid metal nanoparticle composite nanofiber membrane, which comprises the following steps:
(1) separately providing a suspension of liquid metal nanoparticles and an aqueous solution of a polymer;
(2) and (2) mixing the suspension of the liquid metal nano particles obtained in the step (1) with an aqueous solution of a polymer, and carrying out electrostatic spinning to obtain the liquid metal nano particle composite nanofiber membrane.
In the present invention, the sources of the components are not particularly limited, unless otherwise specified, and commercially available products known to those skilled in the art may be used.
The present invention provides a suspension of liquid metal nanoparticles.
In the present invention, the material of the liquid metal nanoparticles preferably includes gallium indium tin alloy or gallium indium alloy. In the invention, the particle size of the liquid metal nanoparticles is preferably 10-1000 nm.
In the present invention, the method for preparing the suspension of liquid metal nanoparticles preferably includes: mixing the liquid metal with a solvent and a stabilizer, and carrying out stirring and/or ultrasonic treatment to obtain a suspension of liquid metal nanoparticles.
In the present invention, the solvent preferably includes absolute ethanol or a mixed solution of ethanol-isopropanol, and more preferably absolute ethanol. In the invention, the ratio of the mass of the liquid metal to the volume of the solvent is preferably 1g (15-25) mL, more preferably 1g (17-22) mL, and most preferably 1g:20 mL. The present invention limits the ratio of the mass of the liquid metal to the volume of the solvent within the above range, and can disperse the liquid metal more uniformly.
In the present invention, the stabilizer preferably includes polyvinylpyrrolidone, polyoxyethylene polyoxypropylene ether F127, dodecanethiol, sodium dodecylbenzenesulfonate or N, N-dimethylacetamide, and more preferably polyvinylpyrrolidone. In the invention, the mass ratio of the stabilizer to the liquid metal is preferably (1-2): 1. the mass ratio of the stabilizer to the liquid metal is limited in the range, so that the liquid metal is more stable, and agglomeration is avoided, and the liquid metal is more uniformly dispersed into the nano fibers.
The operation of mixing the liquid metal with the solvent and the stabilizer is not particularly limited in the present invention, and the technical scheme of mixing materials, which is well known to those skilled in the art, can be adopted.
In the invention, the stirring is preferably mechanical stirring, and the stirring speed is preferably 500-3000 rpm, more preferably 1000-2000 rpm; the stirring time is preferably 1-30 h, more preferably 5-25 h, and most preferably 10-20 h.
In the invention, the power of the ultrasonic wave is preferably 150-250W, and more preferably 180-200W; the ultrasonic time is preferably 10-30 h, more preferably 15-25 h, and most preferably 20 h.
The invention limits the rotation rate and time of stirring and the power and time of ultrasonic wave in the above range, and can make the liquid metal fully split, break and oxidize to form nano-particles. In the present invention, during the stirring and/or ultrasonic process, the liquid metal is broken up and oxidation reaction occurs on the surface of the liquid metal particles, thereby forming a suspension of liquid metal nanoparticles.
In the present invention, the stirring and the ultrasonic treatment are preferably performed separately or alternately.
The invention also provides aqueous solutions of the polymers.
In the present invention, the polymer preferably includes polyvinyl alcohol, polyethylene oxide, polyimide or polyvinylidene fluoride, more preferably includes polyvinyl alcohol or polyethylene oxide; the mass concentration of the aqueous solution of the polymer is preferably 5 to 15%, more preferably 7 to 12%, and most preferably 9 to 11%. The invention limits the types of the polymers and the mass concentration of the aqueous solution of the polymers within the range, can ensure that the aqueous solution of the polymers has more proper viscosity and rheological property, improves the spinnability of electrostatic spinning, does not break to form discrete bead structures or block nozzles during electrostatic spinning, and is drawn into filaments.
In the present invention, the water in the aqueous solution of the polymer is preferably deionized water.
The operation of mixing the polymer and water in the present invention is not particularly limited, and the technical scheme of mixing materials well known to those skilled in the art can be adopted. In the invention, the mixing of the polymer and water is preferably carried out under stirring conditions, the stirring is preferably magnetic stirring, and the stirring speed is preferably 100-300 rpm, more preferably 200 rpm; the stirring time is preferably 1-5 h, and more preferably 2-4 h. The stirring temperature is not particularly limited, and the polymer and water can be fully mixed.
After the mixing of the polymer and water is completed, the present invention preferably subjects the mixed product to defoaming treatment to obtain an aqueous solution of the polymer. In the present invention, the defoaming is preferably vacuum defoaming. The invention has no special limit on the vacuum degree and time of the vacuum defoaming, and can ensure that the aqueous solution of the polymer does not contain bubbles.
After the suspension of the liquid metal nano particles and the aqueous solution of the polymer are obtained, the suspension of the liquid metal nano particles and the aqueous solution of the polymer are mixed for electrostatic spinning, and the liquid metal nano particle composite nanofiber membrane is obtained.
In the invention, the mass ratio of the liquid metal nanoparticles to the polymer is preferably 1 (1-3), and more preferably 1 (1.5-2.5). According to the invention, the mass ratio of the liquid metal nanoparticles to the polymer is limited within the range, so that more liquid metal nanoparticles can be contained in the composite material and the liquid metal nanoparticles can be dispersed more uniformly.
The operation of mixing the suspension of liquid metal nanoparticles and the aqueous solution of the polymer is not particularly limited in the present invention, and the technical scheme of mixing materials, which is well known to those skilled in the art, can be adopted. In the present invention, the mixing of the suspension of liquid metal nanoparticles with the aqueous solution of the polymer is preferably direct mixing or real-time on-line mixing. In the present invention, the direct mixing is preferably performed under stirring conditions, and the stirring is preferably magnetic stirring; the rotating speed of the stirring is preferably 1000-2000 rpm, and more preferably 1500 rpm; the stirring time is preferably 15-25 h, and more preferably 20 h. In the present invention, the real-time on-line mixing is preferably carried out in an active mixer.
In the invention, the spinning voltage of the electrostatic spinning is preferably 7-15 kV, more preferably 9-13 kV, and most preferably 10-11 kV; the receiving distance is preferably 8-15 cm, and more preferably 10-13 cm; the propelling speed is preferably 0.1-0.5 mm/min, and more preferably 0.2-0.4 mm/min; the propulsion means is preferably pressure propulsion, preferably syringe propulsion or pneumatic propulsion. The invention preferably adopts a receiving plate for receiving, and the surface of the receiving plate is preferably adhered with an aluminum foil. The invention limits the spinning voltage, the receiving distance and the advancing speed of electrostatic spinning in the above range, can lead the yarn to be more stable, further ensures that the composite fiber film has better surface morphology structure, and the composite fiber has smaller diameter and is more uniform.
The invention adopts the aqueous solution of the polymer as the electrostatic spinning solution, adds the liquid metal nano-particles into the electrostatic spinning solution, loads the liquid metal nano-particles on the surface of the nano-fibers or embeds the liquid metal nano-particles into the nano-fibers through electrostatic spinning to form the composite nano-fiber membrane with the self-supporting three-dimensional porous structure, has simple preparation process, controls the process parameters such as the dosage of each component and the like, and leads the liquid metal nano-particles to be evenly dispersed in the nano-fibers.
The invention provides the liquid metal nanoparticle composite nanofiber membrane prepared by the preparation method in the technical scheme. In the present invention, the liquid metal nanoparticle composite nanofiber membrane preferably includes nanofibers and liquid metal nanoparticles distributed inside or on the surface of the nanofibers. In the invention, the size of the liquid metal nano-particles is preferably 10-1000 nm; the diameter of the nanofiber is preferably 100nm to 5 μm.
The liquid metal nanoparticle composite nanofiber membrane provided by the invention is smaller in diameter and more uniform, and the liquid metal nanoparticles are more uniformly loaded on the surface of the nanofiber or embedded in the nanofiber.
The invention also provides application of the liquid metal nanoparticle composite nanofiber membrane in Raman detection.
The application of the liquid metal nanoparticle composite nanofiber membrane in the raman detection is not particularly limited, and the technical scheme of the application of the liquid metal nanoparticle composite nanofiber membrane in the raman detection, which is well known to those skilled in the art, can be adopted.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation process flow of the liquid metal nanoparticle composite nanofiber membrane in this embodiment is shown in fig. 1:
(1) adding 1g of gallium indium tin liquid metal into 20mL of absolute ethyl alcohol (the volume ratio of the mass of the gallium indium tin liquid metal to the absolute ethyl alcohol is 1g:20mL), adding 1g of polyvinylpyrrolidone (the mass ratio of the polyvinylpyrrolidone to the gallium indium tin liquid metal is 1:1), stirring at 1000rpm for 5h, and then carrying out 180W ultrasonic treatment for 15h to obtain a liquid metal nanoparticle suspension (the mass concentration is 6%);
(2) adding 1.74g of polyoxyethylene into 20mL of deionized water, magnetically stirring for 4h at room temperature, vacuumizing and removing bubbles to obtain a polyoxyethylene aqueous solution with the mass concentration of 8%;
(3) mixing the liquid metal nanoparticle suspension and a polyoxyethylene aqueous solution in real time on line by adopting an active mixer according to the volume ratio of 1:1 (the mass ratio of the liquid metal nanoparticles to the polyoxyethylene is 1:1.74), and spinning for 3h under the spinning voltage of 12kV, the receiving distance of 12cm and the advancing speed of 0.1mm/min to obtain the liquid metal nanoparticle composite nanofiber membrane.
Example 2
(1) Adding 1g of gallium indium tin liquid metal into 20mL of absolute ethyl alcohol (the volume ratio of the mass of the gallium indium tin liquid metal to the absolute ethyl alcohol is 1g:20mL), adding 1g of polyvinylpyrrolidone (the mass ratio of the polyvinylpyrrolidone to the gallium indium tin liquid metal is 1:1), stirring at 1000rpm for 5h, and then carrying out 180W ultrasonic treatment for 15h to obtain a liquid metal nanoparticle suspension (the mass concentration is 6%);
(2) adding 2.22g of polyvinyl alcohol into 20mL of deionized water, magnetically stirring at room temperature for 15min, heating to 90 ℃, stirring for 2.5h, vacuumizing and removing bubbles to obtain a polyvinyl alcohol aqueous solution with the mass concentration of 10%;
(3) mixing the liquid metal nanoparticle suspension and a polyvinyl alcohol aqueous solution in real time on line by using an active mixer according to the volume ratio of 1:1 (the mass ratio of the liquid metal nanoparticles to the polyvinyl alcohol is 1:2.22), and spinning for 3 hours at the spinning voltage of 10kV, the receiving distance of 10cm and the advancing speed of 0.1mm/min to obtain the liquid metal nanoparticle composite nanofiber membrane.
SEM images of different parts and different magnifications of the liquid metal nanoparticle composite nanofiber membrane prepared in example 1 are tested, and the results are shown in FIGS. 2-4. As can be seen from fig. 2 to 4, the liquid metal nanoparticles are loaded on the surface of the nanofibers or embedded in the nanofibers, the liquid metal nanoparticles are smaller in size and more uniformly distributed, and the nanofibers are smaller in diameter and more uniformly distributed.
The liquid metal nanoparticle composite nanofiber membrane prepared in example 1 was tested for EDS profile and the results are shown in fig. 5. As can be seen from fig. 5, the liquid metal nanoparticle composite nanofiber membrane is rich in C, O, N and Ga elements.
The SEM image of the liquid metal nanoparticle composite nanofiber membrane prepared in example 2 was tested, and the result is shown in fig. 6. As can be seen from fig. 6, the liquid metal nanoparticles are loaded on the surface of the nanofibers or embedded in the nanofibers, the liquid metal nanoparticles have smaller size and are distributed more uniformly, and the nanofibers have smaller diameter and are more uniform.
In conclusion, the preparation method is simple, the liquid metal nanoparticles are uniformly dispersed in the nanofibers, and the diameters of the nanofibers are smaller and more uniform.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a liquid metal nanoparticle composite nanofiber membrane comprises the following steps:
(1) separately providing a suspension of liquid metal nanoparticles and an aqueous solution of a polymer;
(2) and (2) mixing the suspension of the liquid metal nano particles obtained in the step (1) with an aqueous solution of a polymer, and carrying out electrostatic spinning to obtain the liquid metal nano particle composite nanofiber membrane.
2. The method according to claim 1, wherein the liquid metal nanoparticles in step (1) are made of gallium indium tin alloy or gallium indium alloy.
3. The method of manufacturing according to claim 1 or 2, wherein the method of manufacturing the suspension of liquid metal nanoparticles in the step (1) includes: mixing the liquid metal with a solvent and a stabilizer, and carrying out stirring and/or ultrasonic treatment to obtain a suspension of liquid metal nanoparticles.
4. The method of claim 3, wherein the stabilizer comprises polyvinylpyrrolidone, polyoxyethylene polyoxypropylene ether F127, dodecanethiol, sodium dodecylbenzenesulfonate or N, N-dimethylacetamide; the mass ratio of the stabilizer to the liquid metal is (1-2): 1.
5. the preparation method of claim 3, wherein the ratio of the mass of the liquid metal to the volume of the solvent is 1g (15-25) mL.
6. The production method according to claim 1, wherein the polymer in the step (1) comprises polyvinyl alcohol, polyethylene oxide, polyimide or polyvinylidene fluoride; the mass concentration of the aqueous solution of the polymer is 5-15%.
7. The preparation method according to claim 1, wherein the mass ratio of the liquid metal nanoparticles to the polymer in the step (2) is 1 (1-3).
8. The method according to claim 1, wherein the electrospinning in the step (2) has a spinning voltage of 7 to 15kV, a take-up distance of 8 to 15cm, and a forwarding speed of 0.1 to 0.5 mm/min.
9. The liquid metal nanoparticle composite nanofiber membrane prepared by the preparation method as claimed in any one of claims 1 to 8.
10. Use of the liquid metal nanoparticle composite nanofiber membrane of claim 9 in raman detection.
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Cited By (4)
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CN114600904A (en) * | 2022-03-09 | 2022-06-10 | 北京创新爱尚家科技股份有限公司 | Graphene oxide loaded nano titanium dioxide, photocatalytic graphene antibacterial and bacteriostatic fiber and preparation method thereof |
CN115188919A (en) * | 2022-08-22 | 2022-10-14 | 蜂巢能源科技(无锡)有限公司 | Negative plate, preparation method thereof and battery |
CN115233335A (en) * | 2022-09-01 | 2022-10-25 | 青岛大学 | Flexible liquid metal/seaweed composite fiber and preparation method thereof |
CN115971470A (en) * | 2022-12-12 | 2023-04-18 | 广西大学 | Method for preparing liquid metal nanoparticles by ultrasonic stirring method |
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