CN109916880A - A kind of unidirectional electrostatic spinning three-dimensional Raman enhancing substrate and its preparation method and application - Google Patents
A kind of unidirectional electrostatic spinning three-dimensional Raman enhancing substrate and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to optical detection field of material technology, and the present invention relates to a kind of unidirectional electrostatic spinning three-dimensional Raman enhancing substrates and its preparation method and application.It is followed successively by silver nano-grain, PVA clad, silver nano-grain from inside to outside, the average grain diameter of the silver nano-grain on the inside of PVA clad is 72nm, and the average grain diameter of the silver nano-grain on the outside of PVA clad is 7nm.Polyvinyl alcohol@silver nano-grain spinning substrate is prepared by electrospinning process, silver nano-grain is deposited by the method for hot evaporation, obtains polyvinyl alcohol@silver nano-grain/silver nano-grain Raman enhancing substrate.
Description
Technical field
The invention belongs to optical detection field of material technology, and in particular to a kind of unidirectional electrostatic spinning three-dimensional Raman enhancing base
Bottom and its preparation method and application.
Background technique
Disclosing the information of the background technology part, it is only intended to increase understanding of the overall background of the invention, without certainty
It is considered as recognizing or implying in any form that information composition has become existing skill well known to persons skilled in the art
Art.
Raman enhances this physical phenomenon, since it can provide hypersensitive and unmarked chemistry and bioanalysis, closely
The attention of numerous researchers is attracted within several years.Researcher, which has paid many raising Ramans of making great efforts, enhances substrate
Enhance intensity, sensitivity and uniformity.Studies have shown that these indexs depend primarily on noble metal in the effect by laser excitation
The quantity and density of the hot spot of generation.For three-dimensional Raman enhancing substrate is compared to two dimension enhancing substrate, there is biggish specific surface
Product, thus the quantity of hot spot can be increased, while being especially advantageous for the absorption of testing molecule, therefore highly sensitive drawing can be obtained
Graceful enhancing signal.Extensive work mainly realizes two dimension or three-dimensional Raman using high cost, the photoetching technique of complex process at present
Enhance substrate preparation, therefore limits mass production.
Summary of the invention
For above-mentioned problems of the prior art, it is an object of the present invention to provide a kind of unidirectional electrostatic spinnings three
The graceful enhancing substrate of Wella.These indexs of enhancing intensity, sensitivity and the uniformity of Raman enhancing substrate are also easily by metal nano
Shape, size and the periodically influence of structure.Compared to traditional single spherical nanoparticle, the nano particles of certain complexity by
Have Raman enhancing substrate just more in the narrow nano gap of its higher periodicity and ultra-narrow, the bigger hot spot of density.
In order to solve the above technical problems, the technical solution of the present invention is as follows:
On the one hand, a kind of unidirectional electrostatic spinning three-dimensional Raman enhances substrate, and PVA wraps up silver nano-grain, and is formed rodlike
Fiber, the outer surface silver nanoparticles loaded of rod-like fibre form enhancing substrate, and the silver nano-grain of rod-like fibre outer surface is flat
Equal partial size is less than the average grain diameter of silver nano-grain in rod-like fibre.
Ultra-narrow nanometer band gap between the silver nano-grain on the surface PVA not only obtains highdensity lateral hot spot, inside PVA
Silver nano-grain and the plasmon coupling effect of silver nano-grain on surface also obtain highdensity longitudinal hot spot simultaneously.This
Invention introduces corn nanostructure, and the silver nano-grain on the surface PVA is niblet, and it is corn ear that PVA, which wraps up silver nano-grain,.This
Kind corn structure all generates strong electromagnetic field horizontal and vertical, improves hotspot density, and enhancing Raman enhances the sensitive of substrate
Property.To realize the detection of a variety of toxic molecule solution.The present invention realizes for the first time is based on polyvinyl alcohol@silver nano-grain/silver
The preparation of the unidirectional electrostatic spinning Raman enhancing substrate of nano particle.
Preferably, the average grain diameter of the silver nano-grain of PVA package is 72nm.
Preferably, the average grain diameter of the silver nano-grain of the outer surface load of rod-like fibre is 7nm.
Second aspect, a kind of preparation method of unidirectional electrostatic spinning three-dimensional Raman enhancing substrate, specific steps are as follows: elargol is molten
Liquid is mixed with polyvinyl alcohol water solution, and polyvinyl alcohol@silver nano-grain (PVA@Ag is prepared by electrospinning process
Nanofibers) spinning substrate deposits silver by the method for hot evaporation on the surface of PVA@Ag nanofibers spinning substrate and receives
Rice grain obtains polyvinyl alcohol@silver nano-grain/silver nano-grain (PVA@Agnanofibers/AgNPs) Raman enhancing base
Bottom.
The substrate that polyvinyl alcohol wraps up silver nano-grain is obtained by the method for electrostatic spinning, is then coated in polyvinyl alcohol
The outside deposition silver nano-grain of layer obtains three-dimensional Raman enhancing substrate.Make silver nano-grain chaining by electrospinning process
Shape arrangement, obtains soft Raman enhancing substrate, and PVA plays the silver nano-grain and outside that inside is isolated as clad
The effect of silver nano-grain, compared in the preparation of existing SERS substrate, using PVA as a kind of dispersion stabilizer, in the present invention
PVA is also used as a kind of separation layer, and the silver nano-grain of inside and the silver nano-grain in outside in this way can generate plasma coupling
Effect is closed, and obtains highdensity longitudinal hot spot, while can respectively play a role.To realize a variety of toxic molecule solution
Detection.
The preparation method of above-mentioned unidirectional electrostatic spinning three-dimensional Raman enhancing substrate, specific steps are as follows:
The preparation of fulmargin: heating into container when reagent is added, and the addition sequence of reagent is ethylene glycol, PVP, nitre
Sour silver after constant temperature processing, carries out ice bath processing, acetone is added during ice bath, is then centrifuged, is separated, water is added, is super
Sound obtains fulmargin；
The preparation of PVA aqueous solution: PVA powder is soluble in water, obtain PVA aqueous solution；
The preparation of PVA@Ag nanofibers spinning substrate: obtained fulmargin and PVA aqueous solution are mixed, will be mixed
It closes solution and carries out electrostatic spinning, obtain polyvinyl alcohol@silver nano-grain spinning substrate；
Filamentary silver is deposited on to the surface of spinning substrate by the method for hot evaporation, obtains PVA@Agnanofibers/AgNPs
Raman enhances substrate.
Preferably, in the preparation process of fulmargin, ethylene glycol is first added in room temperature, and PVP is added after being heated to 70-80 DEG C,
Silver nitrate is added after being heated to 120-125 DEG C；Preferably, the temperature of constant temperature processing is 130-135 DEG C；Preferably, separation process
To pour out supernatant liquor；Preferably, the volume of the corresponding ethylene glycol of 1g silver nitrate is 35-45mL；Preferably, silver nitrate and PVP
Mass ratio be 4-6:1；Preferably, the volume of the corresponding acetone of 1g silver nitrate is 50-70mL.
The preparation process of fulmargin reaches the partial size of the silver in fulmargin by the control of reaction condition in the present invention
It is 72nm to average grain diameter, passes through the PVA@Ag that PVA clad cladding is prepared of condition during electrostatic spinning
Nanofibers spinning substrate, compared with the prior art in PVA and silver nano-grain prepare the direct silver nanoparticles loaded of PVA
Electrospinning process it is different, by the way that electrostatic spinning will be carried out after PVA and fulmargin premixing in the present invention, it is complete to obtain PVA
The structure of full cladding silver nano-grain.
Preferably, the temperature in the preparation process of PVA aqueous solution is 70-90 DEG C, and the time of stirring is 5-7h；Preferably,
The mass fraction of PVA aqueous solution is 10-20%.
Preferably, in the preparation process of PVA@Ag nanofibers spinning substrate, PVA aqueous solution and fulmargin press body
Product compares 1:1.5-2.5.
Preferably, the process of electrostatic spinning are as follows: prepare negative electrode, PVA aqueous solution and fulmargin mixed solution are packed into
Syringe, syringe connection anode, obtains PVA@for the surface that mixed solution is injected into negative electrode using syringe
Agnanofibers/AgNPs Raman enhances substrate.
It is further preferred that the distance between syringe needle point and negative electrode are 9-11cm；It is further preferred that voltage is
11-13kV；It is further preferred that syringe driving velocity is 1.5-2.5mm/h；It is further preferred that the spinning time is 15-
25min。
Preferably, the diameter of filamentary silver is 0.15-0.25mm in hot evaporation.
The third aspect, application of the above-mentioned unidirectional electrostatic spinning three-dimensional Raman enhancing substrate in Raman detection.
The nanofibrous structures of one-dimensional order of the present invention also improve the stability of substrate.In addition, prepared by the SERS substrate
Method is nontoxic and pollution-free, easy to operate, can also realize and directly prepare in irregular curved base surface, for a variety of toxic
Mixed molecules solution detection；
Unidirectional electrostatic spinning three-dimensional Raman enhancing substrate of the invention detects crystal violet, is limited to 10 to the detection of crystal violet-10, lower, the high sensitivity of detection limit, stability is good, and homogeneity is high；Detection is limited to 10 in detection malachite green-9；From detection the Sudan
The Raman enhanced spectrum figure of red I, CV, MG mixed solution is available, and three-dimensional Raman enhancing substrate of the invention can mix
Individual molecule is detected in molecule.
Detailed description of the invention
The Figure of description for constituting a part of the invention is used to provide further understanding of the present invention, and of the invention shows
Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.
Fig. 1 is that the embodiment of the present invention 1, embodiment 2, embodiment 3 or embodiment 4 prepare polyvinyl alcohol@silver nano-grain/silver
The schematic diagram of the unidirectional electrostatic spinning three-dimensional Raman enhancing substrate of nano particle.
Fig. 2 is that the embodiment of the present invention 1 prepares the unidirectional electrostatic spinning three-dimensional of polyvinyl alcohol@silver nano-grain/silver nano-grain
Raman enhances the scanning electron microscope image of the different multiples of substrate.
Fig. 3 is that the embodiment of the present invention 1 prepares the unidirectional electrostatic spinning three-dimensional of polyvinyl alcohol@silver nano-grain/silver nano-grain
The Raman enhanced spectrum figure of Raman enhancing substrate acquisition crystal violet (CV): (a) 10-5-10-10The Raman spectrum of the CV molecule of M concentration
Figure；(b) the 10 of 10 points detection are randomly choosed in this SERS substrate-6The CV Molecular Raman spectrogram of M concentration.
Fig. 4 is that the embodiment of the present invention 1 prepares the unidirectional electrostatic spinning three-dimensional of polyvinyl alcohol@silver nano-grain/silver nano-grain
Raman enhances the Raman enhanced spectrum figure that substrate obtains malachite green (MG).
Fig. 5 (a) is that the embodiment of the present invention 1 prepares flexible polyethylene alcohol@silver nano-grain/unidirectional Static Spinning of silver nano-grain
The three-dimensional Raman enhancing substrate of silk is used to detect the photo of Sudan red 1, CV, MG mixed solution；(b) it is carried out for the present invention in curved surface former
Position electrostatic spinning prepares the unidirectional electrostatic spinning three-dimensional Raman enhancing substrate of flexible polyethylene alcohol@silver nano-grain/silver nano-grain
Detect the Raman enhanced spectrum figure of mixed molecules.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the present invention.Unless another
It indicates, all technical and scientific terms used herein has usual with general technical staff of the technical field of the invention
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to exemplary embodiments of the present invention.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
As shown in Figure 1, illustrating the preparation process of Raman enhancing substrate of the invention, PVA and fulmargin mixing are put into
In syringe, two sections of copper adhesive tapes are pasted on the glass sheet as negative electrode, syringe connects positive electrode, and electrostatic spinning obtains spinning
Substrate, hot evaporation deposit silver nano-grain on the surface of spinning substrate, obtain the Raman enhancing substrate of corn ear structure.
Below with reference to embodiment, the present invention is further described
Embodiment 1
A kind of unidirectional electrostatic spinning three-dimensional Raman enhancing substrate of flexible polyethylene alcohol@silver nano-grain/silver nano-grain
Preparation method, including following preparation step:
It prepares fulmargin: clean flask is put into oil cauldron, 135 DEG C of temperature of heating setting；40mL ethylene glycol is added；Add
Heat adds 0.5gPVP (55000) to 75 DEG C；125 DEG C are heated to, 0.1g silver nitrate is added；In one hour of 135 DEG C of constant temperature；It takes out
Ice bath afterwards is centrifuged after 60mL acetone precipitation then is added, and pours out supernatant and deionized water ultrasound is added；It is repeated three
It is secondary, obtain fulmargin；
Preparation PVA aqueous solution: PVA powder is dissolved in deionized water, is obtained within 6 hours in 80 DEG C of at a temperature of stirring
The PVA aqueous solution of 15wt%；
Prepare electrostatic spinning precursor liquid: by PVA aqueous solution and fulmargin, 1:2 is mixed by volume, is sufficiently stirred 1
Hour obtains uniform mixed solution, and injects in the syringe of 10mL；
Electrostatic spinning: it is separated by 1cm on clean sheet glass and pastes two sections of copper adhesive tapes in parallel as negative electrode, 19G is not
The steel needle head that becomes rusty accesses syringe, connects positive electrode, and the distance of needle point to substrate is 10cm, voltage 12kV, syringe promotion speed
Degree is 2mm/h, and the spinning time is 20min, obtains the polyvinyl alcohol@silver nano-grain spinning substrate of one-dimensional order.
Substrate is curved surface in the present embodiment, and substrate can be plane in other embodiments.
It is silver-plated: the filamentary silver that the diameter of 1mm long is 0.2mm being passed through into hot evaporation on the surface of spinning substrate, obtains polyethylene
The unidirectional electrostatic spinning Raman of alcohol@silver nano-grain/silver nano-grain enhances substrate.
The scanning electron microscope (SEM) photograph of obtained Raman enhancing substrate is as shown in Fig. 2, as shown in Figure 2, the present invention, which has been prepared, to be received
Rice fiber, the diameter of nanofiber are about 100nm, and the diameter of the silver nano-grain of PVA package is about 72nm；The Yin Na of hot evaporation
The diameter of rice grain is about 7nm.
Embodiment 2
A kind of unidirectional electrostatic spinning three-dimensional Raman enhancing substrate of flexible polyethylene alcohol@silver nano-grain/silver nano-grain
Preparation method, including following preparation step:
It prepares fulmargin: clean flask is put into oil cauldron, 135 DEG C of temperature of heating setting；40mL ethylene glycol is added；Add
Heat adds 0.5gPVP (55000) to 70 DEG C；125 DEG C are heated to, 0.1g silver nitrate is added；In one hour of 135 DEG C of constant temperature；It takes out
Ice bath afterwards is centrifuged after 60mL acetone precipitation then is added, and pours out supernatant and deionized water ultrasound is added；It is repeated three
It is secondary, obtain fulmargin；
Preparation PVA aqueous solution: PVA powder is dissolved in deionized water, is obtained within 6 hours in 80 DEG C of at a temperature of stirring
The PVA aqueous solution of 15wt%；
Prepare electrostatic spinning precursor liquid: by PVA aqueous solution and fulmargin, 1:1.5 is mixed by volume, is sufficiently stirred
It mixes 1 hour and obtains uniform mixed solution, and inject in the syringe of 10mL；
Electrostatic spinning: it is separated by 1cm on clean sheet glass and pastes two sections of copper adhesive tapes in parallel as negative electrode, 19G is not
The steel needle head that becomes rusty accesses syringe, connects positive electrode, and the distance of needle point to substrate is 9cm, voltage 12kV, syringe driving velocity
For 2mm/h, the spinning time is 20min, obtains the polyvinyl alcohol@silver nano-grain spinning substrate of one-dimensional order.
It is silver-plated: the filamentary silver that the diameter of 1mm long is 0.2mm being passed through into hot evaporation on the surface of spinning substrate, obtains polyethylene
The unidirectional electrostatic spinning Raman of alcohol@silver nano-grain/silver nano-grain enhances substrate.Obtained Raman enhancing substrate is compared to implementation
The thickness of the Raman enhancing substrate PVA clad of example 1 thickens, and the diameter of nanofiber is thicker.
Embodiment 3
A kind of unidirectional electrostatic spinning three-dimensional Raman enhancing substrate of flexible polyethylene alcohol@silver nano-grain/silver nano-grain
Preparation method, including following preparation step:
It prepares fulmargin: clean flask is put into oil cauldron, 135 DEG C of temperature of heating setting；40mL ethylene glycol is added；Add
Heat arrives 70-80 DEG C, adds 0.5gPVP (55000)；125 DEG C are heated to, 0.1g silver nitrate is added；In one hour of 135 DEG C of constant temperature；
Ice bath after taking-up is centrifuged after 60mL acetone precipitation then is added, and pours out supernatant and deionized water ultrasound is added；It is repeated
Three times, fulmargin is obtained；
Preparation PVA aqueous solution: PVA powder is dissolved in deionized water, is obtained within 6 hours in 80 DEG C of at a temperature of stirring
The PVA aqueous solution of 15wt%；
Prepare electrostatic spinning precursor liquid: by PVA aqueous solution and fulmargin, 1:2 is mixed by volume, is sufficiently stirred 1
Hour obtains uniform mixed solution, and injects in the syringe of 10mL；
Electrostatic spinning: it is separated by 1cm on clean sheet glass and pastes two sections of copper adhesive tapes in parallel as negative electrode, 19G is not
The steel needle head that becomes rusty accesses syringe, connects positive electrode, and the distance of needle point to substrate is 10cm, voltage 12kV, syringe promotion speed
Degree is 2mm/h, and the spinning time is 20min, obtains the polyvinyl alcohol@silver nano-grain spinning substrate of one-dimensional order.
It is silver-plated: the filamentary silver that the diameter of 1mm long is 0.15mm being passed through into hot evaporation on the surface of spinning substrate, obtains polyethylene
The unidirectional electrostatic spinning Raman of alcohol@silver nano-grain/silver nano-grain enhances substrate.Obtained Raman enhancing substrate and embodiment 1
It compares, the partial size of the silver nano-grain of PVA layer surface becomes smaller.
Embodiment 4
A kind of unidirectional electrostatic spinning three-dimensional Raman enhancing substrate of flexible polyethylene alcohol@silver nano-grain/silver nano-grain
Preparation method, including following preparation step:
It prepares fulmargin: clean flask is put into oil cauldron, 135 DEG C of temperature of heating setting；40mL ethylene glycol is added；Add
Heat adds 0.5gPVP (55000) to 80 DEG C；120 DEG C are heated to, 0.1g silver nitrate is added；In one hour of 130 DEG C of constant temperature；It takes out
Ice bath afterwards is centrifuged after 60mL acetone precipitation then is added, and pours out supernatant and deionized water ultrasound is added；It is repeated three
It is secondary, obtain fulmargin；
Preparation PVA aqueous solution: PVA powder is dissolved in deionized water, is obtained within 6 hours in 75 DEG C of at a temperature of stirring
The PVA aqueous solution of 15wt%；
Prepare electrostatic spinning precursor liquid: by PVA aqueous solution and fulmargin, 1:2 is mixed by volume, is sufficiently stirred 1
Hour obtains uniform mixed solution, and injects in the syringe of 10mL；
Electrostatic spinning: it is separated by 1cm on clean sheet glass and pastes two sections of copper adhesive tapes in parallel as negative electrode, 19G is not
The steel needle head that becomes rusty accesses syringe, connects positive electrode, and the distance of needle point to substrate is 10cm, voltage 12kV, syringe promotion speed
Degree is 2mm/h, and the spinning time is 20min, obtains the polyvinyl alcohol@silver nano-grain spinning substrate of one-dimensional order.
It is silver-plated: the filamentary silver that the diameter of 1mm long is 0.2mm being passed through into hot evaporation on the surface of spinning substrate, obtains polyethylene
The unidirectional electrostatic spinning Raman of alcohol@silver nano-grain/silver nano-grain enhances substrate.Compared with Example 1, the Yin Na on the inside of PVA
The partial size of rice grain is larger, is 85nm.
The Raman enhancing substrate that embodiment 2- embodiment 4 is prepared enhances substrate, detection compared to the Raman of embodiment 1
Accuracy is lower, and the detection limit to crystal violet is respectively 10-9M, 10-8M, 10-9M。
Test example 1
The Raman enhancing substrate obtained using embodiment 1 carries out Raman detection, test to the crystal violet (CV) of various concentration
Parameter is 532nm laser, 0.48mW power, 600gr/nm grating, the 8s time of integration.As a result as shown in figure 3, by Fig. 3 a it is found that
Raman enhancing substrate prepared by the present invention can be to 10-5-10-10The CV molecule of M concentration is sensitively detected, by Fig. 3 b it is found that
Detectability distribution everywhere in substrate is relatively uniform.
Test example 2
The Raman enhancing substrate obtained using embodiment 1 carries out Raman detection to the malachite green (MG) of various concentration, surveys
Examination parameter is 532nm laser, 0.48mW power, 600gr/nm grating, the 8s time of integration.As a result as shown in figure 4, as shown in Figure 4,
Raman enhancing substrate prepared by the present invention can be to 10-5-10-9The malachite green (MG) of M concentration is sensitively detected.
Test example 3
The Raman enhancing substrate obtained using embodiment 1 is to 10-6The Sudan red 1 of M, 10-9The CV of M and 10-7The MG of M is mixed
Solution carries out Raman detection, and test parameter is 532nm laser, 0.48mW power, 600gr/nm grating, the 8s time of integration.As a result
As shown in figure 5, as shown in Figure 5, Raman enhancing substrate prepared by the present invention can carry out spirit to Sudan red 1, CV, MG mixed solution
Quick detection can respectively obtain the Raman spectrum of tri- kinds of Sudan red 1, CV, MG substances.Illustrate that Raman substrate of the invention can
Single molecule is detected in mixed molecules, it was demonstrated that its great potential produced in batches in situ in arbitrary surfaces, Neng Goujin
The accurate in situ detection of row labyrinth.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of unidirectional electrostatic spinning three-dimensional Raman enhances substrate, it is characterised in that: PVA wraps up silver nano-grain, and forms stick
Shape fiber, the outer surface silver nanoparticles loaded of rod-like fibre form enhancing substrate, the silver nano-grain of rod-like fibre outer surface
Average grain diameter is less than the average grain diameter of silver nano-grain in rod-like fibre；
Preferably, the average grain diameter of the silver nano-grain of PVA package is 72nm；
Preferably, the average grain diameter of the silver nano-grain of the outer surface load of rod-like fibre is 7nm.
2. a kind of preparation method of unidirectional electrostatic spinning three-dimensional Raman enhancing substrate, it is characterised in that: specific steps are as follows: elargol is molten
Liquid is mixed with polyvinyl alcohol water solution, and polyvinyl alcohol@silver nano-grain spinning substrate is prepared by electrospinning process,
The surface of PVA@Ag nanofibers spinning substrate deposits silver nano-grain by the method for hot evaporation, obtains polyvinyl alcohol@silver
Nano particle/silver nano-grain Raman enhances substrate.
3. preparation method according to claim 2, it is characterised in that: specific steps are as follows:
The preparation of fulmargin: heating into container when reagent is added, and the addition sequence of reagent is ethylene glycol, PVP, nitric acid
Silver after constant temperature processing, carries out ice bath processing, acetone is added during ice bath, is then centrifuged, separated, water, ultrasound is added
Obtain fulmargin；
The preparation of PVA aqueous solution: PVA powder is soluble in water, obtain PVA aqueous solution；
The preparation of PVA@Ag nanofibers spinning substrate: obtained fulmargin and PVA aqueous solution are mixed, will be mixed molten
Liquid carries out electrostatic spinning, obtains polyvinyl alcohol@silver nano-grain spinning substrate；
Filamentary silver is deposited on to the surface of spinning substrate by the method for hot evaporation, obtains PVA@Agnanofibers/AgNPs Raman
Enhance substrate；
Preferably, in the preparation process of fulmargin, ethylene glycol is first added in room temperature, and PVP is added after being heated to 70-80 DEG C, heating
Silver nitrate is added after to 120-125 DEG C；Preferably, the temperature of constant temperature processing is 130-135 DEG C；Preferably, separation process is to fall
Supernatant liquor out；Preferably, the volume of the corresponding ethylene glycol of 1g silver nitrate is 35-45mL；Preferably, the matter of silver nitrate and PVP
Amount is than being 4-6:1.
4. preparation method according to claim 3, it is characterised in that: the volume of the corresponding acetone of 1g silver nitrate is 50-
70mL。
5. preparation method according to claim 3, it is characterised in that: the temperature in the preparation process of PVA aqueous solution is 70-
90 DEG C, the time of stirring is 5-7h；Preferably, the mass fraction of PVA aqueous solution is 10-20%.
6. preparation method according to claim 3, it is characterised in that: the preparation of PVA@Ag nanofibers spinning substrate
In the process, PVA aqueous solution and fulmargin 1:1.5-2.5 by volume.
7. preparation method according to claim 3, it is characterised in that: the process of electrostatic spinning are as follows: prepare negative electrode, it will
PVA aqueous solution and fulmargin mixed solution are packed into syringe, and syringe connection anode is injected mixed solution using syringe
PVA@Agnanofibers/AgNPs Raman enhancing substrate is obtained to the surface of negative electrode.
8. preparation method according to claim 3, it is characterised in that: the distance between syringe needle point and negative electrode are 9-
11cm；It is further preferred that voltage is 11-13kV；It is further preferred that syringe driving velocity is 1.5-2.5mm/h；Into one
Step is preferred, and the spinning time is 15-25min.
9. preparation method according to claim 3, it is characterised in that: the diameter of filamentary silver is 0.15-0.25mm in hot evaporation.
10. application of the unidirectional electrostatic spinning three-dimensional Raman enhancing substrate described in claim 1 in Raman detection.
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| 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 |
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| CN112525881A (en) * | 2020-11-17 | 2021-03-19 | 宁夏大学 | Polyvinyl alcohol coated surface enhanced Raman scattering substrate and preparation method thereof |
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