CN109916880B - Unidirectional electrostatic spinning three-dimensional Raman enhanced substrate and preparation method and application thereof - Google Patents
Unidirectional electrostatic spinning three-dimensional Raman enhanced substrate and preparation method and application thereof Download PDFInfo
- Publication number
- CN109916880B CN109916880B CN201910325424.8A CN201910325424A CN109916880B CN 109916880 B CN109916880 B CN 109916880B CN 201910325424 A CN201910325424 A CN 201910325424A CN 109916880 B CN109916880 B CN 109916880B
- Authority
- CN
- China
- Prior art keywords
- silver
- electrospun
- enhanced substrate
- substrate
- pva
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Artificial Filaments (AREA)
Abstract
The invention belongs to the technical field of optical detection materials, and relates to a unidirectional electrostatic spinning three-dimensional Raman enhanced substrate, and a preparation method and application thereof. The silver nanoparticle, the PVA coating layer and the silver nanoparticle are sequentially arranged from inside to outside, the average particle size of the silver nanoparticle on the inner side of the PVA coating layer is 72nm, and the average particle size of the silver nanoparticle on the outer side of the PVA coating layer is 7 nm. The polyvinyl alcohol @ silver nanoparticle spinning substrate is prepared through an electrostatic spinning method, and the silver nanoparticles are deposited through a thermal evaporation method to obtain the polyvinyl alcohol @ silver nanoparticles/silver nanoparticles Raman enhanced substrate.
Description
Technical Field
The invention belongs to the technical field of optical detection materials, and particularly relates to a unidirectional electrostatic spinning three-dimensional Raman enhanced substrate, and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Raman enhancement, a physical phenomenon that has attracted the attention of a large number of researchers in recent years, has provided ultrasensitive and label-free chemical and biological analyses. Researchers have made many efforts to improve the enhancement intensity, sensitivity and uniformity of raman-enhanced substrates. Studies have shown that these criteria depend mainly on the number and density of hot spots generated by the action of the laser excitation of the noble metal. Compared with a two-dimensional enhanced substrate, the three-dimensional Raman enhanced substrate has larger specific surface area, so that the number of heating points can be increased, and the absorption of molecules to be detected is facilitated, so that a Raman enhanced signal with high sensitivity can be obtained. At present, a great deal of work is mainly carried out by adopting a photoetching technology with high cost and complex process to realize the preparation of a two-dimensional or three-dimensional Raman enhanced substrate, so that the mass production is limited.
Disclosure of Invention
In view of the above-mentioned problems occurring in the prior art, it is an object of the present invention to provide a unidirectional electrospun three-dimensional raman-enhanced substrate. These indicators of enhanced intensity, sensitivity, and uniformity of the raman-enhanced substrate are also highly susceptible to the shape, size, and periodicity of the metal nanostructures. Compared with the traditional single spherical nanoparticles, some complex nanoparticles have more hot spots with higher density on the Raman enhancement substrate due to the higher periodicity and the ultra-narrow nano gap.
In order to solve the technical problems, the technical scheme of the invention is as follows:
on the one hand, the one-way electrostatic spinning three-dimensional Raman reinforced substrate is characterized in that PVA wraps silver nanoparticles and forms rod-shaped fibers, silver nanoparticles are loaded on the outer surfaces of the rod-shaped fibers to form the reinforced substrate, and the average particle size of the silver nanoparticles on the outer surfaces of the rod-shaped fibers is smaller than that of the silver nanoparticles in the rod-shaped fibers.
The ultra-narrow nanometer band gap between the silver nanometer particles on the surface of the PVA not only obtains a high-density transverse hot spot, but also obtains a high-density longitudinal hot spot simultaneously due to the plasma coupling effect of the silver nanometer particles in the PVA and the silver nanometer particles on the surface. The invention introduces a corn nano structure, the silver nano particles on the surface of PVA are corn grains, and the silver nano particles coated by PVA are corn cobs. The corn structure generates strong electromagnetic fields in the transverse direction and the longitudinal direction, thereby improving the hot spot density and enhancing the sensitivity of the Raman enhanced substrate. Thereby realizing the detection of various toxic molecule solutions. The preparation method disclosed by the invention realizes the preparation of the Raman-enhanced substrate based on the polyvinyl alcohol @ silver nanoparticles/silver nanoparticles through unidirectional electrostatic spinning for the first time.
Preferably, the PVA-coated silver nanoparticles have an average particle size of 72 nm.
Preferably, the silver nanoparticles supported on the outer surface of the rod-shaped fiber have an average particle diameter of 7 nm.
In a second aspect, a preparation method of a unidirectional electrostatic spinning three-dimensional Raman enhanced substrate comprises the following specific steps: mixing a silver colloid solution and a polyvinyl alcohol aqueous solution, preparing a polyvinyl alcohol @ silver nanoparticle (PVA @ Ag nanofibers) spinning substrate by an electrostatic spinning method, and depositing silver nanoparticles on the surface of the PVA @ Ag nanoparticles spinning substrate by a thermal evaporation method to obtain a polyvinyl alcohol @ silver nanoparticle/silver nanoparticle (PVA @ AgNAfibers/AgNPs) Raman enhancement substrate.
And obtaining a substrate with silver nano particles wrapped by polyvinyl alcohol through an electrostatic spinning method, and then depositing the silver nano particles on the outer surface of the polyvinyl alcohol coating to obtain the three-dimensional Raman enhanced substrate. The method comprises the steps of arranging silver nanoparticles in a chain shape through an electrostatic spinning method to obtain a soft Raman enhancement substrate, and taking PVA as a coating layer to play a role in isolating the silver nanoparticles on the inner side from the silver nanoparticles on the outer side. Thereby realizing the detection of various toxic molecule solutions.
The preparation method of the unidirectional electrostatic spinning three-dimensional Raman enhanced substrate comprises the following specific steps:
preparing a silver colloid solution: adding a reagent into a container while heating, wherein the adding sequence of the reagent comprises ethylene glycol, PVP and silver nitrate, carrying out ice bath treatment after constant temperature treatment, adding acetone during the ice bath treatment, and then carrying out centrifugation, separation, water addition and ultrasonic treatment to obtain a silver colloid solution;
preparation of aqueous PVA solution: dissolving PVA powder in water to obtain a PVA aqueous solution;
preparation of PVA @ Ag nanofibers spinning substrate: mixing the obtained silver colloid solution with a PVA (polyvinyl alcohol) aqueous solution, and performing electrostatic spinning on the mixed solution to obtain a polyvinyl alcohol @ silver nanoparticle spinning substrate;
and depositing the silver wires on the surface of the spinning substrate by a thermal evaporation method to obtain the PVA @ Agnanofibrers/AgNPs Raman enhanced substrate.
Preferably, in the preparation process of the silver colloid solution, firstly adding ethylene glycol at room temperature, heating to 70-80 ℃, then adding PVP, heating to 120-125 ℃, and then adding silver nitrate; preferably, the temperature of the constant temperature treatment is 130-135 ℃; preferably, the separation process is to pour out the supernatant; preferably, the volume of the glycol corresponding to 1g of silver nitrate is 35-45 mL; preferably, the mass ratio of silver nitrate to PVP is 4-6: 1; preferably, 1g of silver nitrate corresponds to a volume of 50-70mL of acetone.
According to the preparation method, the reaction condition is controlled in the preparation process of the silver colloid solution, so that the average particle size of silver in the silver colloid solution is 72nm, the PVA @ Ag nanofibres spinning substrate coated with the PVA coating layer is prepared through condition control in the electrostatic spinning process, and compared with the electrostatic spinning method for preparing PVA directly loaded with silver nanoparticles by PVA and silver nanoparticles in the prior art, the preparation method is different in that the PVA and the silver colloid solution are premixed and then subjected to electrostatic spinning, so that the structure of the PVA completely coated with the silver nanoparticles is obtained.
Preferably, the temperature in the preparation process of the PVA aqueous solution is 70-90 ℃, and the stirring time is 5-7 h; preferably, the PVA aqueous solution is 10 to 20 mass percent.
Preferably, during the preparation of the PVA @ Ag nanofibres spinning substrate, the volume ratio of the PVA aqueous solution to the silver colloid solution is 1: 1.5-2.5.
Preferably, the electrostatic spinning process comprises: preparing a negative electrode, filling the mixed solution of the PVA aqueous solution and the silver colloid solution into an injector, connecting the injector with the positive electrode, and injecting the mixed solution to the surface of the negative electrode by using the injector to obtain the PVA @ Agnanofibrers/AgNPs Raman enhanced substrate.
Further preferably, the distance between the needle tip of the syringe and the negative electrode is 9-11 cm; further preferably, the voltage is 11-13 kV; further preferably, the pushing speed of the injector is 1.5-2.5 mm/h; more preferably, the spinning time is 15 to 25 min.
Preferably, the diameter of the silver wire in thermal evaporation is 0.15-0.25 mm.
In a third aspect, the one-way electrospun three-dimensional Raman enhanced substrate is applied to Raman detection.
The unidirectional ordered nanofiber structure of the invention also improves the stability of the substrate. In addition, the preparation method of the SERS substrate is non-toxic and pollution-free, is simple to operate, can realize direct preparation on the surface of an irregular curved substrate, and is used for detecting various toxic mixed molecular solutions;
the unidirectional electrostatic spinning three-dimensional Raman enhanced substrate provided by the invention is used for detecting crystal violet, and the detection limit of the crystal violet is 10-10The detection limit is low, the sensitivity is high, the stability is good, and the uniformity is high; the detection limit in the detection of malachite green is 10-9(ii) a The three-dimensional Raman enhancement substrate can detect single molecules in mixed molecules by detecting the Raman enhancement spectrogram of the Sudan red I, CV and MG mixed solution.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
Fig. 1 is a schematic illustration of the preparation of polyvinyl alcohol @ silver nanoparticles/silver nanoparticles unidirectional electrospun three-dimensional raman enhanced substrate of example 1, example 2, example 3 or example 4 of the present invention.
Fig. 2 is a scanning electron microscope image of different magnification of polyvinyl alcohol @ silver nanoparticle/silver nanoparticle unidirectional electrospun three-dimensional raman enhanced substrate prepared in example 1 of the present invention.
FIG. 3 shows the present inventionExample 1 preparation of polyvinyl alcohol @ silver nanoparticles/silver nanoparticles unidirectional electrospinning of a three-dimensional raman enhanced substrate a raman enhanced spectrogram of Crystal Violet (CV) was obtained: (a) 10. the method of the present invention-5-10-10Raman spectra of CV molecules at M concentration; (b) randomly selecting 10 points on the SERS substrate for detection 10-6Raman spectrum of CV molecules at M concentration.
Fig. 4 is a raman enhancement spectrum of Malachite Green (MG) obtained by preparing a polyvinyl alcohol @ silver nanoparticle/silver nanoparticle unidirectional electrospinning three-dimensional raman enhancement substrate in example 1 of the present invention.
Fig. 5(a) is a photo of flexible polyvinyl alcohol @ silver nanoparticle/silver nanoparticle unidirectional electrospinning three-dimensional raman-enhanced substrate prepared in example 1 of the present invention for detecting sudan red I, CV and MG mixed solution; (b) in the invention, in-situ electrostatic spinning is carried out on a curved surface to prepare a Raman enhanced spectrogram of the flexible polyvinyl alcohol @ silver nano-particle/silver nano-particle unidirectional electrostatic spinning three-dimensional Raman enhanced substrate detected mixed molecules.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As shown in fig. 1, the preparation process of the raman-enhanced substrate of the present invention is shown, PVA and silver colloid solution are mixed and put into an injector, two sections of copper adhesive tapes are pasted on a glass sheet as a negative electrode, the injector is connected with a positive electrode, a spinning substrate is obtained by electrostatic spinning, silver nanoparticles are deposited on the surface of the spinning substrate by thermal evaporation, and the raman-enhanced substrate with a corn cob structure is obtained.
The invention will be further illustrated by the following examples
Example 1
A preparation method of a flexible polyvinyl alcohol @ silver nanoparticle/silver nanoparticle unidirectional electrostatic spinning three-dimensional Raman enhanced substrate comprises the following preparation steps:
preparing a silver colloid solution: putting the clean flask into an oil pan, and heating to a set temperature of 135 ℃; adding 40mL of ethylene glycol; heating to 75 deg.C, adding 0.5g PVP (55000); heating to 125 deg.C, adding 0.1g silver nitrate; keeping the temperature at 135 ℃ for one hour; taking out, carrying out ice bath, adding 60mL of acetone for precipitation, centrifuging, pouring out supernate, and adding deionized water for ultrasound; repeating the steps for three times to obtain a silver colloid solution;
preparation of aqueous PVA solution: dissolving PVA powder in deionized water, and stirring at 80 ℃ for 6 hours to obtain 15 wt% PVA aqueous solution;
preparing electrostatic spinning precursor solution: mixing the PVA aqueous solution and the silver colloid solution according to the volume ratio of 1:2, fully stirring for 1 hour to obtain a uniform mixed solution, and injecting the uniform mixed solution into a 10mL injector;
electrostatic spinning: two sections of copper adhesive tapes are pasted on a clean glass sheet in parallel at an interval of 1cm and used as negative electrodes, a 19G stainless steel needle is connected with an injector and connected with a positive electrode, the distance from the needle to a substrate is 10cm, the voltage is 12kV, the pushing speed of the injector is 2mm/h, and the spinning time is 20min, so that the unidirectional ordered polyvinyl alcohol @ silver nanoparticle spinning substrate is obtained.
In this embodiment, the substrate is a curved surface, and in other embodiments, the substrate may be a flat surface.
Silver plating: and (3) carrying out thermal evaporation on the surface of the spinning substrate by using silver wires with the length of 1mm and the diameter of 0.2mm to obtain the polyvinyl alcohol @ silver nano particles/silver nano particles unidirectional electrostatic spinning Raman enhanced substrate.
The scanning electron microscope image of the obtained raman-enhanced substrate is shown in fig. 2, and as can be seen from fig. 2, the nanofiber prepared by the method has the diameter of about 100nm, and the silver nanoparticle coated with PVA has the diameter of about 72 nm; the diameter of the thermally evaporated silver nanoparticles was about 7 nm.
Example 2
A preparation method of a flexible polyvinyl alcohol @ silver nanoparticle/silver nanoparticle unidirectional electrostatic spinning three-dimensional Raman enhanced substrate comprises the following preparation steps:
preparing a silver colloid solution: putting the clean flask into an oil pan, and heating to a set temperature of 135 ℃; adding 40mL of ethylene glycol; heating to 70 deg.C, adding 0.5g PVP (55000); heating to 125 deg.C, adding 0.1g silver nitrate; keeping the temperature at 135 ℃ for one hour; taking out, carrying out ice bath, adding 60mL of acetone for precipitation, centrifuging, pouring out supernate, and adding deionized water for ultrasound; repeating the steps for three times to obtain a silver colloid solution;
preparation of aqueous PVA solution: dissolving PVA powder in deionized water, and stirring at 80 ℃ for 6 hours to obtain 15 wt% PVA aqueous solution;
preparing electrostatic spinning precursor solution: mixing the PVA aqueous solution and the silver colloid solution according to the volume ratio of 1:1.5, fully stirring for 1 hour to obtain a uniform mixed solution, and injecting the uniform mixed solution into a 10mL injector;
electrostatic spinning: two sections of copper adhesive tapes are pasted on a clean glass sheet in parallel at an interval of 1cm and used as negative electrodes, a 19G stainless steel needle is connected with an injector and connected with a positive electrode, the distance from the needle to a substrate is 9cm, the voltage is 12kV, the pushing speed of the injector is 2mm/h, and the spinning time is 20min, so that the unidirectional ordered polyvinyl alcohol @ silver nanoparticle spinning substrate is obtained.
Silver plating: and (3) carrying out thermal evaporation on the surface of the spinning substrate by using silver wires with the length of 1mm and the diameter of 0.2mm to obtain the polyvinyl alcohol @ silver nano particles/silver nano particles unidirectional electrostatic spinning Raman enhanced substrate. The thickness of the obtained raman-enhanced substrate was thicker than that of the PVA coating layer of the raman-enhanced substrate of example 1, and the diameter of the nanofiber was thicker.
Example 3
A preparation method of a flexible polyvinyl alcohol @ silver nanoparticle/silver nanoparticle unidirectional electrostatic spinning three-dimensional Raman enhanced substrate comprises the following preparation steps:
preparing a silver colloid solution: putting the clean flask into an oil pan, and heating to a set temperature of 135 ℃; adding 40mL of ethylene glycol; heating to 70-80 deg.C, adding 0.5g PVP (55000); heating to 125 deg.C, adding 0.1g silver nitrate; keeping the temperature at 135 ℃ for one hour; taking out, carrying out ice bath, adding 60mL of acetone for precipitation, centrifuging, pouring out supernate, and adding deionized water for ultrasound; repeating the steps for three times to obtain a silver colloid solution;
preparation of aqueous PVA solution: dissolving PVA powder in deionized water, and stirring at 80 ℃ for 6 hours to obtain 15 wt% PVA aqueous solution;
preparing electrostatic spinning precursor solution: mixing the PVA aqueous solution and the silver colloid solution according to the volume ratio of 1:2, fully stirring for 1 hour to obtain a uniform mixed solution, and injecting the uniform mixed solution into a 10mL injector;
electrostatic spinning: two sections of copper adhesive tapes are pasted on a clean glass sheet in parallel at an interval of 1cm and used as negative electrodes, a 19G stainless steel needle is connected with an injector and connected with a positive electrode, the distance from the needle to a substrate is 10cm, the voltage is 12kV, the pushing speed of the injector is 2mm/h, and the spinning time is 20min, so that the unidirectional ordered polyvinyl alcohol @ silver nanoparticle spinning substrate is obtained.
Silver plating: and (3) carrying out thermal evaporation on the surface of the spinning substrate by using 1mm long silver wires with the diameter of 0.15mm to obtain the polyvinyl alcohol @ silver nano particles/silver nano particles unidirectional electrostatic spinning Raman enhanced substrate. Compared with example 1, the particle size of the silver nanoparticles on the surface of the PVA layer of the obtained Raman-enhanced substrate is smaller.
Example 4
A preparation method of a flexible polyvinyl alcohol @ silver nanoparticle/silver nanoparticle unidirectional electrostatic spinning three-dimensional Raman enhanced substrate comprises the following preparation steps:
preparing a silver colloid solution: putting the clean flask into an oil pan, and heating to a set temperature of 135 ℃; adding 40mL of ethylene glycol; heating to 80 deg.C, adding 0.5g PVP (55000); heating to 120 deg.C, adding 0.1g silver nitrate; keeping the temperature at 130 ℃ for one hour; taking out, carrying out ice bath, adding 60mL of acetone for precipitation, centrifuging, pouring out supernate, and adding deionized water for ultrasound; repeating the steps for three times to obtain a silver colloid solution;
preparation of aqueous PVA solution: dissolving PVA powder in deionized water, and stirring at 75 ℃ for 6 hours to obtain 15 wt% PVA aqueous solution;
preparing electrostatic spinning precursor solution: mixing the PVA aqueous solution and the silver colloid solution according to the volume ratio of 1:2, fully stirring for 1 hour to obtain a uniform mixed solution, and injecting the uniform mixed solution into a 10mL injector;
electrostatic spinning: two sections of copper adhesive tapes are pasted on a clean glass sheet in parallel at an interval of 1cm and used as negative electrodes, a 19G stainless steel needle is connected with an injector and connected with a positive electrode, the distance from the needle to a substrate is 10cm, the voltage is 12kV, the pushing speed of the injector is 2mm/h, and the spinning time is 20min, so that the unidirectional ordered polyvinyl alcohol @ silver nanoparticle spinning substrate is obtained.
Silver plating: and (3) carrying out thermal evaporation on the surface of the spinning substrate by using silver wires with the length of 1mm and the diameter of 0.2mm to obtain the polyvinyl alcohol @ silver nano particles/silver nano particles unidirectional electrostatic spinning Raman enhanced substrate. The silver nanoparticles inside the PVA had a larger particle size of 85nm compared to example 1.
In examples 2 to 4, the raman-enhanced substrate prepared in example 1 has lower detection accuracy than the raman-enhanced substrate prepared in example 1, and the detection limits for crystal violet are 10-9M，10-8M，10-9M。
Test example 1
The Raman enhanced substrate obtained in the embodiment 1 is used for carrying out Raman detection on Crystal Violet (CV) with different concentrations, and the testing parameters are 532nm laser, 0.48mW power, 600gr/nm grating and 8s integration time. As shown in FIG. 3, it can be seen from FIG. 3a that the Raman-enhanced substrate prepared by the present invention can be paired with the Raman-enhanced substrate 10-5-10-10The CV molecules at M concentration were sensitively detected, and as can be seen from FIG. 3b, the distribution of the detection ability was relatively uniform throughout the substrate.
Test example 2
Raman detection is carried out on Malachite Green (MG) with different concentrations by using the Raman enhancement substrate obtained in the embodiment 1, and the testing parameters are 532nm laser, 0.48mW power, 600gr/nm grating and 8s integration time. As shown in FIG. 4, it can be seen from FIG. 4 that the Raman-enhanced substrate prepared by the present invention can be paired with the Raman-enhanced substrate 10-5-10-9Sensitive detection of M-concentration Malachite Green (MG)。
Test example 3
Raman-enhanced substrate pair 10 obtained in example 1 was used-6Sudan red I, 10 of M-9CV and 10 of M-7And performing Raman detection on the MG mixed solution of M, wherein the test parameters are 532nm laser, 0.48mW power, 600gr/nm grating and 8s integration time. As shown in fig. 5, it can be seen from fig. 5 that the raman-enhanced substrate prepared by the present invention can sensitively detect the sudan red I, CV and MG mixed solution, and can obtain raman spectra of the sudan red I, CV and MG, respectively. The Raman substrate can detect single molecules in mixed molecules, proves the great potential of the Raman substrate in-situ batch production on any surface, and can carry out accurate in-situ detection on complex structures.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (14)
1. A unidirectional electrospun three-dimensional Raman enhanced substrate is characterized in that: PVA wraps the silver nanoparticles to form rod-shaped fibers, the silver nanoparticles are loaded on the outer surfaces of the rod-shaped fibers to form a reinforced substrate, and the average particle size of the silver nanoparticles on the outer surfaces of the rod-shaped fibers is smaller than that of the silver nanoparticles in the rod-shaped fibers;
the preparation method of the unidirectional electrostatic spinning three-dimensional Raman reinforced substrate comprises the following specific steps: mixing a silver colloid solution and a polyvinyl alcohol aqueous solution, preparing a polyvinyl alcohol @ silver nanoparticle spinning substrate by an electrostatic spinning method, and depositing silver nanoparticles on the surface of the polyvinyl alcohol @ silver nanoparticle spinning substrate by a thermal evaporation method to obtain a polyvinyl alcohol @ silver nanoparticle/silver nanoparticle Raman enhanced substrate;
the preparation method of the silver colloid solution comprises the following steps: adding a reagent into a container while heating, wherein the adding sequence of the reagent comprises ethylene glycol, PVP and silver nitrate, carrying out ice bath treatment after constant temperature treatment, adding acetone during the ice bath treatment, and then carrying out centrifugation, separation, water addition and ultrasonic treatment to obtain a silver colloid solution;
the method comprises the following specific steps: adding ethylene glycol at room temperature, heating to 70-80 ℃, then adding PVP, heating to 120-125 ℃, and then adding silver nitrate; the temperature of the constant temperature treatment is 130-135 ℃; the separation process is to pour out the supernatant; the volume of the glycol corresponding to 1g of silver nitrate is 35-45 mL; the mass ratio of silver nitrate to PVP is 4-6: 1.
2. the uniaxially electrospun three-dimensional raman enhanced substrate according to claim 1, wherein: the average particle size of the PVA-coated silver nanoparticles was 72 nm.
3. The uniaxially electrospun three-dimensional raman enhanced substrate according to claim 1, wherein: the silver nanoparticles supported on the outer surface of the rod-shaped fiber had an average particle diameter of 7 nm.
4. The uniaxially electrospun three-dimensional raman enhanced substrate according to claim 1, wherein: preparation of aqueous PVA solution: dissolving PVA powder in water to obtain a PVA aqueous solution;
preparation of polyvinyl alcohol @ silver nanoparticle spinning substrate: mixing the obtained silver colloid solution with a PVA (polyvinyl alcohol) aqueous solution, and performing electrostatic spinning on the mixed solution to obtain a polyvinyl alcohol @ silver nanoparticle spinning substrate;
and depositing the silver filaments on the surface of the spinning substrate by a thermal evaporation method to obtain the polyvinyl alcohol @ silver nanoparticle/silver nanoparticle Raman enhanced substrate.
5. The uniaxially electrospun three-dimensional raman enhanced substrate according to claim 4, wherein: the temperature in the preparation process of the PVA aqueous solution is 70-90 ℃, and the stirring time is 5-7 h.
6. The uniaxially electrospun three-dimensional raman enhanced substrate according to claim 5, wherein: the mass fraction of the PVA aqueous solution is 10-20%.
7. The uniaxially electrospun three-dimensional raman enhanced substrate according to claim 4, wherein: in the preparation process of the polyvinyl alcohol @ silver nanoparticle spinning substrate, the PVA aqueous solution and the silver colloid solution are in a volume ratio of 1: 1.5-2.5.
8. The uniaxially electrospun three-dimensional raman enhanced substrate according to claim 1, wherein: the electrostatic spinning process comprises the following steps: preparing a negative electrode, filling the mixed solution of the PVA aqueous solution and the silver colloid solution into an injector, connecting the injector with the positive electrode, and injecting the mixed solution to the surface of the negative electrode by using the injector to obtain the polyvinyl alcohol @ silver nanoparticle/silver nanoparticle Raman-enhanced substrate.
9. The uniaxially electrospun three-dimensional raman enhanced substrate according to claim 8, wherein: the distance between the needle point of the syringe and the negative electrode is 9-11 cm.
10. The uniaxially electrospun three-dimensional raman enhanced substrate according to claim 8, wherein: the voltage is 11-13 kV.
11. The uniaxially electrospun three-dimensional raman enhanced substrate according to claim 8, wherein: the pushing speed of the injector is 1.5-2.5 mm/h.
12. The uniaxially electrospun three-dimensional raman enhanced substrate according to claim 8, wherein: the spinning time is 15-25 min.
13. The uniaxially electrospun three-dimensional raman enhanced substrate according to claim 1, wherein: the diameter of the silver wire in the thermal evaporation is 0.15-0.25 mm.
14. Use of the uniaxially electrospun three-dimensional raman-enhanced substrate of any one of claims 1-13 for raman detection.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910325424.8A CN109916880B (en) | 2019-04-22 | 2019-04-22 | Unidirectional electrostatic spinning three-dimensional Raman enhanced substrate and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910325424.8A CN109916880B (en) | 2019-04-22 | 2019-04-22 | Unidirectional electrostatic spinning three-dimensional Raman enhanced substrate and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109916880A CN109916880A (en) | 2019-06-21 |
| CN109916880B true CN109916880B (en) | 2021-07-20 |
Family
ID=66978147
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910325424.8A Active CN109916880B (en) | 2019-04-22 | 2019-04-22 | Unidirectional electrostatic spinning three-dimensional Raman enhanced substrate and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109916880B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111366572A (en) * | 2020-03-27 | 2020-07-03 | 苏州聚龙能源科技有限公司 | Method for quantitatively analyzing content of graphene in graphene composite conductive slurry |
| CN112525881A (en) * | 2020-11-17 | 2021-03-19 | 宁夏大学 | Polyvinyl alcohol coated surface enhanced Raman scattering substrate and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102677212A (en) * | 2012-06-01 | 2012-09-19 | 苏州大学 | Surface-enhanced Raman scattering active substrate and preparation method thereof |
| WO2013171542A1 (en) * | 2012-05-14 | 2013-11-21 | Pontificia Universidad Catolica De Chile | Polymer-metallic nanoparticle hybrid materials |
| CN103411946A (en) * | 2013-06-24 | 2013-11-27 | 吉林大学 | Method for preparing surface-enhanced Raman spectrum base by using electrospinning technique |
| CN103741259A (en) * | 2014-01-16 | 2014-04-23 | 齐齐哈尔大学 | Fluorene-triphenylamine copolymer/graphene composite nano-fiber material with shell-core structure |
| CN105002657A (en) * | 2015-03-26 | 2015-10-28 | 长春理工大学 | Porous polymer-Ag composite film serving as SERS substrate |
| CN106637679A (en) * | 2016-12-08 | 2017-05-10 | 清华大学 | Micro-nano fiber arrays and preparation method and device thereof |
| EP3165511A1 (en) * | 2015-11-03 | 2017-05-10 | The State Scientific Institution "Institute of Chemistry of New Materials of National Academy of Sciences of Belarus" | Method for producing a polymer film with a high concentration of silver nanoparticles |
| CN109060762A (en) * | 2018-07-27 | 2018-12-21 | 山东师范大学 | Composite and flexible surface enhanced Raman substrate based on silver nano-grain and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101406969B1 (en) * | 2013-05-10 | 2014-06-20 | 한국과학기술연구원 | Manufacturing method of solid-state dye-sensitized solar cells and electrolyte filling device used therefor |
| TWI565852B (en) * | 2015-05-11 | 2017-01-11 | Acelon Chem & Fiber Corp | Preparation of Nano silver blended natural cellulose fibers method |
-
2019
- 2019-04-22 CN CN201910325424.8A patent/CN109916880B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013171542A1 (en) * | 2012-05-14 | 2013-11-21 | Pontificia Universidad Catolica De Chile | Polymer-metallic nanoparticle hybrid materials |
| CN102677212A (en) * | 2012-06-01 | 2012-09-19 | 苏州大学 | Surface-enhanced Raman scattering active substrate and preparation method thereof |
| CN103411946A (en) * | 2013-06-24 | 2013-11-27 | 吉林大学 | Method for preparing surface-enhanced Raman spectrum base by using electrospinning technique |
| CN103741259A (en) * | 2014-01-16 | 2014-04-23 | 齐齐哈尔大学 | Fluorene-triphenylamine copolymer/graphene composite nano-fiber material with shell-core structure |
| CN105002657A (en) * | 2015-03-26 | 2015-10-28 | 长春理工大学 | Porous polymer-Ag composite film serving as SERS substrate |
| EP3165511A1 (en) * | 2015-11-03 | 2017-05-10 | The State Scientific Institution "Institute of Chemistry of New Materials of National Academy of Sciences of Belarus" | Method for producing a polymer film with a high concentration of silver nanoparticles |
| CN106637679A (en) * | 2016-12-08 | 2017-05-10 | 清华大学 | Micro-nano fiber arrays and preparation method and device thereof |
| CN109060762A (en) * | 2018-07-27 | 2018-12-21 | 山东师范大学 | Composite and flexible surface enhanced Raman substrate based on silver nano-grain and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| "One-step synthesis of size-tunable Ag nanoparticles incorporated in electrospun PVA/cyclodextrin nanofibers";Asli Celebioglu,et al.;《Carbohydrate Polymers》;20130907;第808-816页 * |
| "SERS activated platform with three-dimensional hot spots and tunable nanometer gap";Chao Zhang et al.;《Sensors and Actuators B》;20171120;第163-171页 * |
| "Three-Dimensional Surface-Enhanced Raman Scattering Substrate Fabricated by Chemical Decoration of Silver Nanoparticles on Electrospun Polycarbonate Nanofibers";Murugesan Balamurugan，et al.;《Applied Spectroscopy》;20161231;第1-9页 * |
| "静电纺丝法制备纳米抗菌纤维的研究进展";张志杰 等;《化学研究》;20160131;第27卷(第1期);第12-20页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109916880A (en) | 2019-06-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Huang et al. | Nanotubular SnO2 templated by cellulose fibers: synthesis and gas sensing | |
| Yang et al. | Hydrogen-bond-mediated in situ fabrication of AgNPs/Agar/PAN electrospun nanofibers as reproducible SERS substrates | |
| Yang et al. | Fabrication of Ag@ TiO2 electrospinning nanofibrous felts as SERS substrate for direct and sensitive bacterial detection | |
| Brinson et al. | Nanoshells made easy: improving Au layer growth on nanoparticle surfaces | |
| Aliheidari et al. | Electrospun nanofibers for label-free sensor applications | |
| Kim et al. | One-dimensional arrangement of gold nanoparticles by electrospinning | |
| Shi et al. | Preparation of band gap tunable SnO2 nanotubes and their ethanol sensing properties | |
| Ryu et al. | Synthesis of diphenylalanine/cobalt oxide hybrid nanowires and their application to energy storage | |
| Hu et al. | Fabrication, characterization, and application in SERS of self-assembled polyelectrolyte− gold nanorod multilayered films | |
| Severyukhina et al. | Nanoplasmonic chitosan nanofibers as effective SERS substrate for detection of small molecules | |
| Zhang et al. | Electrospinning nanoparticles-based materials interfaces for sensor applications | |
| Tang et al. | Photoinduced shape conversion and reconstruction of silver nanoprisms | |
| Wang et al. | Synthesis and characterization of water-soluble and bifunctional ZnO− Au nanocomposites | |
| Aslan et al. | Fast and slow deposition of silver nanorods on planar surfaces: application to metal-enhanced fluorescence | |
| Drew et al. | Metal oxide-coated polymer nanofibers | |
| Chen et al. | Surface-enhanced Raman detection of melamine on silver-nanoparticle-decorated silver/carbon nanospheres: effect of metal ions | |
| Athauda et al. | Systematic study of the structure–property relationships of branched hierarchical TiO2/ZnO nanostructures | |
| Mali et al. | Novel synthesis and characterization of mesoporous ZnO nanofibers by electrospinning technique | |
| Yi et al. | Patterned growth of vertically aligned silicon nanowire arrays for label-free DNA detection using surface-enhanced Raman spectroscopy | |
| CN109916880B (en) | Unidirectional electrostatic spinning three-dimensional Raman enhanced substrate and preparation method and application thereof | |
| CN107059160B (en) | The graphene fiber and preparation method thereof of nanometer modified by silver | |
| Wang et al. | Photochemical synthesis of ZnO/Ag heterogeneous nanostructure on chemically patterned ferroelectric crystals for high performance SERS detection | |
| Tang et al. | Seed-mediated electroless deposition of gold nanoparticles for highly uniform and efficient SERS enhancement | |
| Kong et al. | Highly enhanced Raman scattering with good reproducibility observed on a flexible PI nanofabric substrate decorated by silver nanoparticles with controlled size | |
| Satheeshkumar et al. | Photochemical decoration of silver nanoparticles on ZnO nanowires as a three‐dimensional substrate for surface‐enhanced Raman scattering measurement |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |