CN102677212B - Surface-enhanced Raman scattering active substrate and preparation method thereof - Google Patents
Surface-enhanced Raman scattering active substrate and preparation method thereof Download PDFInfo
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- CN102677212B CN102677212B CN2012101784924A CN201210178492A CN102677212B CN 102677212 B CN102677212 B CN 102677212B CN 2012101784924 A CN2012101784924 A CN 2012101784924A CN 201210178492 A CN201210178492 A CN 201210178492A CN 102677212 B CN102677212 B CN 102677212B
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- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000758 substrate Substances 0.000 title claims abstract description 21
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 87
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 81
- 239000002105 nanoparticle Substances 0.000 claims abstract description 78
- 229910001316 Ag alloy Inorganic materials 0.000 claims abstract description 43
- 239000002121 nanofiber Substances 0.000 claims abstract description 38
- 238000009987 spinning Methods 0.000 claims abstract description 27
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 3
- 230000000694 effects Effects 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 101710134784 Agnoprotein Proteins 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000010931 gold Substances 0.000 abstract description 101
- 239000000243 solution Substances 0.000 abstract description 65
- 229910052737 gold Inorganic materials 0.000 abstract description 22
- 229910052709 silver Inorganic materials 0.000 abstract description 16
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 abstract description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 11
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 10
- 239000004332 silver Substances 0.000 abstract description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 abstract description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 abstract description 4
- 239000001509 sodium citrate Substances 0.000 abstract description 4
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- 230000009467 reduction Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
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- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
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- 239000002904 solvent Substances 0.000 description 3
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 3
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- 229910001020 Au alloy Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
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- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
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Abstract
The invention relates to a surface-enhanced Raman scattering active substrate and a preparation method thereof. A HAuCl4 solution and a AgNO3 solution are added in a polyvinyl alcohol aqueous solution with a certain mass concentration, then sodium citrate is added to prepare a polyvinyl alcohol/Au-Ag alloy nanoparticle spinning solution after sufficient reaction, and a parallel type electrostatic spinning technology is adopted to obtain the surface-enhanced Raman scattering active substrate with a polyvinyl alcohol/Au-Ag alloy nanoparticle composite nanofiber structure, wherein the content of Au-Ag alloy nanoparticles is 2*10<-4> to 2*10<-2> mol/g, and the molar ratio of Au:Ag is (1:2)-(1:3). As gold-silver alloy nanoparticles can absorb light from blue to green and the plasma resonance wavelength can be controlled and adjusted between silver and gold, the applicable wavelength range of the surface-enhanced Raman scattering active substrate material provided by the invention is wider than that of a gold or silver single-component substrate.
Description
Technical field
The present invention relates to a kind of optical measurement material and preparation method thereof, particularly a kind of surface-enhanced Raman scattering activity base material and preparation method thereof.
Background technology
From Fleischmann after the silver electrode surface of electrochemical roughening has found that the Raman signal of pyridine is greatly strengthened, the special surface of metal nanoparticle strengthens the sensitivity that surperficial humidification that optical property is subject to people's great attention, especially gold/silver nano particle can greatly improve analyzing and testing.Gold/silver nano particle internal freedom electronics regular motion and the surface plasma body resonant vibration that produces, because plasmon is confined to a very little zone, makes this regional electric field greatly strengthen under the external electromagnetic field action of certain frequency.Utilize this highfield effect, the efficiency of many two-phonon process is significantly improved, as surface-enhanced Raman, surface strengthens fluorescence and surface strengthens infrared.The lip-deep Raman signal enhancing of precious metal is called as SERS (Surface Enhanced Raman Scattering, SERS).The electromagnetic field mechanism of SERS is thought, existence with type free electronic metal substrate of certain surface roughness, the larger enhancing of electromagnetic field that makes incident laser produce on surface, and the intensity of Raman scattering and molecule optical electric field of living in square become legal, therefore increase greatly the molecule that is adsorbed on surface and produced the probability of Raman scattering, thereby improved the surperficial raman scattering intensity that detects.Increasing substantially of this detection sensitivity makes one of its detection means that is called emerging unimolecule science.
At present, the active substrate of SERS comprises solid substrate, the metal-sol that coarse metal electrode, metal film cover and utilizes substrate that metal-sol builds etc.Electrostatic spinning technique is a kind of simple direct method for preparing nano-scale fiber, when polymer solution or the lip-deep electric power of polymer melt overcome its surface tension, charged jet generation sprays, jet is crooked after stretching in line, and then follow the loop wire spiral and advance, solvent evaporates or melt solidify, on the receiver that very thin nanofiber is collected in ground is connected.In recent years, a kind of nano fibrous membrane of using electrospinning process preparation receives much concern as the research of SERS base material, this method is carried out the polymer nanofiber that contains gold or Nano silver grain that electrostatic spinning makes after adopting polymer and nm of gold or nano-Ag particles blend, as document ACS Nano, 2009 (3): 3993-4002, Thin solid films, 2010 (518): 3228-3233 has introduced respectively employing PVA/Ag, and the PMMA/Au nanofiber is used for the SERS base material.Adopt its outstanding advantage of nanofiber of electrostatic spinning preparation to be its high-specific surface area, when this makes it as the SERS substrate,, for absorption analyte molecule provides more site, effectively increase the contact surface with detection material, thereby increase substantially the sensitivity of detection.At present, the nano fibrous membrane that is used for the SERS base material adopts polymer nanofiber and golden nanometer particle or Nano silver grain blend more and obtains.
It has been generally acknowledged that, surface plasma is stronger, and is stronger at the electromagnetic field on surface, and the corresponding Raman enhancement effect of generation is also larger.Exciting light and two factors of substrate are depended in the acquisition of surface plasma, and can whether the plasma resonance peak of excitation wavelength and substrate mates will cause obtaining stronger Surface field, thereby directly affect the intensity of SERS.For single gold or Nano silver grain, can be by regulating gold/silver nano particle size and concentration or the regrowth method by gold/galactic nucleus can change its plasma resonance frequency, but changeable being limited in scope.
Summary of the invention
The object of the invention is to overcome the deficiency that prior art exists, provide a kind of gold-silver alloy nanoparticles concentration high, good dispersion, applicable wavelengths is in extensive range, surface-enhanced Raman scattering activity base material that combination property is excellent and preparation method thereof.
Realize that the technical scheme of the object of the invention is to provide a kind of preparation method of surface-enhanced Raman scattering activity substrate, comprises the steps:
(1) adding molar concentration in mass concentration is 0.5～2% polyvinyl alcohol water solution is the HAuCl of 0.1～5 mmol/L
4And AgNO
3Solution, by mole densimeter, Au:Ag is 1:2～1:3, is heated to boiling; Adding mass concentration in reaction system is 0.2～0.5% natrium citricum, and under the boiling condition, fully reaction, obtain Au-Ag alloy nano particle colloidal solution;
The Au-Ag alloy nano particle colloidal solution eccentric cleaning that (2) will prepare, add polyvinyl alcohol water solution, controlling the polyvinyl alcohol mass concentration is 8～10%, the molar concentration of Au-Ag alloy nano particle is 0.01～0.1 mol/L, fully mix under stirring condition, obtain polyvinyl alcohol/Au-Ag alloy nano particle spinning solution;
(3) adopt the electrostatic spinning apparatus of run-in index, spinning voltage is 8～14 kV, and the distance between spinning mouth and receiving screen is 8～15 cm, obtains a kind of surface-enhanced Raman scattering activity substrate.
2, the surface-enhanced Raman scattering activity base material that obtains by claim 1 preparation method is characterized in that: it is polyvinyl alcohol/Au-Ag alloy nano particle composite nano fiber, and by mole densimeter, the content of Au-Ag alloy nano particle is 2 * 10
-4～2 * 10
-2Mol/g, in molar ratio, Au:Ag is 1:2～1:3.
Owing to having implemented technique scheme, compared with prior art, the beneficial effect that the present invention obtains is:
1, because the gold-silver alloy nano particle all can occur absorbing in green glow at blue light, its plasma resonance wavelength can carry out controllable adjustment between silver (370nm) and gold (530nm).Therefore, the present invention adopts the gold-silver alloy nano particle with different plasma resonance frequencies as base material, and its applicable wave-length coverage is more extensive than the substrate of gold and silver one pack system.
2, traditional gold-silver alloy nano particle preparation methods that adopt Link, namely in aqueous phase system, by coreduction gold chloride (HAuCl more
4) and silver nitrate (AgNO
3) and obtain.But for fear of the generation of AgCl precipitation, this reaction is generally carried out in weak solution.Utilize the nano particle number deficiency of the method preparation to obtain intensive nano particle on nanofiber, can't produce surface enhanced effect required " hot-zone (Hot-Spot) ".And polyvinyl alcohol is a kind of good water-soluble polymer, has a large amount of hydroxyls, and in poly-vinyl alcohol solution, the present invention, take natrium citricum as reductant, is used for reduction HAuCl
4And AgNO
3Mixed solution, with HAuCl
4And AgNO
3Fast restore is gold-silver alloy nanoparticles, adopts the concentration of the gold-silver alloy nanoparticles of this method preparation will be apparently higher than traditional coreduction method, and gold-silver alloy nanoparticles can be scattered in polymer solution well.
3, the present invention will reduce and prepare the gold-silver alloy nano particle in polymer solution, and polymer solution is carried out the electrospun nanofibers film.Polyvinyl alcohol (PVA) is not only protective agent, and is used for the matrix material as Electrospun, can make between metal nanoparticle and matrix material good compatibility is arranged, and material has more excellent combination property.
Description of drawings
Fig. 1 is that the reduction in the polyvinyl alcohol water solution of variable concentrations that the embodiment of the present invention provides obtains the ultra-violet absorption spectrum comparison diagram of Au-Ag alloy nano particle;
Fig. 2 is the HAuCl of the same amount that provides of the embodiment of the present invention
4And AgNO
3The ultra-violet absorption spectrum comparison diagram of the Au-Ag alloy nano particle that reduction obtains in water and PVA solution respectively;
Fig. 3 is the ultraviolet-visible absorption spectroscopy comparison diagram of the contained Au that provides of the embodiment of the present invention alloy nano particle different with the Ag ratio;
Fig. 4 is the TEM photo comparison diagram of the PVA/Au-Ag nanofiber of the contained Au that provides of the embodiment of the present invention alloy nano particle different with the Ag ratio;
Fig. 5 is the surface plasmon resonance absorption wavelength comparison diagram of the contained Au that provides of the embodiment of the present invention PVA/Au-Ag nanofiber different with the Ag ratio;
Fig. 6 is the SERS comparison diagram of the contained Ag that provides of the embodiment of the present invention PVA different with the Au ratio/Au-Ag nanofiber;
Fig. 7 is that the different PVA/Au-Ag nanofiber of Au-Ag content that the embodiment of the present invention provides contrasts the SERS collection of illustrative plates of mercaptobenzoic acid (4-MBA) respectively;
Fig. 8 is the PVA/Au that the embodiment of the present invention provides
1Ag
3The SERS collection of illustrative plates contrast of nanofiber and drop-cast film.
The specific embodiment
Technical solution of the present invention is further elaborated below in conjunction with drawings and Examples.
Synthesizing of gold-silver alloy nanoparticles
2.4 g polyvinyl alcohol (PVA) are joined in 13.6 g water, slowly be warming up to 80 ℃, heated 1 hour, PVA dissolves fully, and the PVA solution that obtains presents the sticking homogeneous solution of water white transparency tool, and the mass fraction of PVA solution is 15%.
The preparation quality mark is respectively 1%, 5%, and the PVA solution of three kinds of variable concentrations of 10%, as the solution of reduction preparation gold-silver alloy nanoparticles, in the PVA of variable concentrations solution, enters respectively HAuCl
4(2 mmol, 6 mL) and AgNO
3(2 mmol, 6mL), then be heated to boiling, the sodium citrate solution (accounting for 0.3 % of reaction system) that adds respectively again mass concentration 1 % of 5 mL, continue boiling 2 h, obtain gold-silver alloy nanoparticles/PVA solution, gold-silver alloy nanoparticles wherein, the mol ratio of Jin Yuyin are that 1:1(is denoted as Au
1Ag
1).
Referring to accompanying drawing 1, it is that the reduction in the polyvinyl alcohol water solution of variable concentrations that the present embodiment provides obtains the ultra-violet absorption spectrum comparison diagram that the Au-Ag mol ratio is the alloy nano particle of 1:1; Polyvinyl alcohol water solution is respectively 1 wt%, 5 wt%, 10 wt%.Result by Fig. 1 shows, Au
1Ag
1The surface plasmon resonance absorption wavelength of alloy nano particle between Au and Ag, has confirmed Au
1Ag
1The successful preparation of alloy nano particle.And at the surface plasma resonance peak of the synthetic Au-Ag alloy nano particle of the PVA solution of 5 wt% and 10 wt%, be not Au
1Ag
1, but the position at the surface plasma resonance peak of Au nano particle.This shows, the PVA solution of 1 wt% is the optimum condition of synthetic Au-Ag alloy nano particle.
Au with preparation
1Ag
1Alloy nano particle colloidal solution under the rotating speed of 6000 rpm centrifugal three times, each 25 minutes, to remove unreacted metal salt solution.Then add ultra-pure water and again disperse, be diluted to 0.6 mL.Then the PVA solution that adds 10 wt% of 2.4 mL, stir at normal temperatures, fully mixes.Gained PVA concentration is 8 wt%, Au
1Ag
3Alloy nano particle is the spinning solution of 4 mmol, is used for electrostatic spinning.
Adopt the electrostatic spinning apparatus of run-in index, by the slow pushing syringe of syringe pump, solution is extruded.With Au
1Ag
1/ PVA spinning solution is placed in the syringe of 10 mL, and the parameter adjustment of syringe pump is that the discharge rate of spinning solution is 0.3 mL/h.Spinning voltage is 12 kV, and the distance between spinning mouth and receiving screen is 10 cm, obtains PVA/Au
1Ag
1Nanofiber, Au
1Ag
1Content be 4 * 10
-5Mol/g.
PVA/Au
1Ag
1The performance of nanofiber is referring to shown in accompanying drawing 3～5.
Comparative Examples 1: will with the HAuCl of the above-mentioned same amount of the present embodiment
4And AgNO
3After mixing under the condition that exists without PVA, add reductant, prepare the Au-Ag alloy nano particle.
Referring to accompanying drawing 2, it is the HAuCl of the same amount that provides of the present embodiment
4And AgNO
3The ultra-violet absorption spectrum comparison diagram of the Au-Ag alloy nano particle that (Comparative Examples 1) reduction obtains in PVA solution and water respectively; As seen from Figure 2, in PVA the position at the surface plasma resonance peak of synthetic Au-Ag alloy nano particle with synthetic very close of aqueous phase, but UV intensity obviously goes out by force nearly 10 times.
Embodiment 2:
2.4 g polyvinyl alcohol (PVA) are joined in 13.6 g water, slowly be warming up to 80 ℃, heated 1 hour, PVA dissolves fully, and the PVA solution that obtains presents the sticking homogeneous solution of water white transparency tool, and the mass fraction of PVA solution is 15%.
In being 1% PVA solution, mass concentration adds respectively the HAuCl as table 1 proportional arrangement
4(2 mmol) and AgNO
3(2 mmol), namely the mol ratio of Au and Ag is respectively 0:1,1:1,2:1,3:1,1:0; Then be heated to boiling, then add respectively the sodium citrate solution (accounting for 0.3 % of reaction system) of mass concentration 1 % of 5 mL, continue boiling 2 h, obtain the PVA/Au-Ag nano-particle solution, the alloy nano particle of the synthetic Au-Ag different proportion of reduction, meter is made Ag, Au successively
1Ag
1, Au
2Ag
1, Au
3Ag
1And Au.
Table 1
| Nanoparticle | HAuCl 4 (2 mmol, mL) | AgNO 3 (2 mmol, mL) |
| Ag | 0 | 12 |
| Au 1Ag 1 | 6 | 6 |
| Au 2Ag 1 | 8 | 4 |
| Au 3Ag 1 | 9 | 3 |
| Au | 12 | 0 |
Will be by each gold-silver alloy nanoparticles colloidal solution of the proportioning of table 1 preparation, under the rotating speed of 6000 rpm centrifugal three times respectively, each 25 minutes, to remove unreacted metal salt solution.Then add ultra-pure water and again disperse, be diluted to 0.6 mL.Add again the PVA solution of 10 wt% of 2.4 mL, stir at normal temperatures 5 h, fully mix.Gained Au-Ag content is 4mmol but Au alloy nano particle, the PVA mass concentration different from the Ag ratio is the spinning solution of 8 wt%.
Adopt the electrostatic spinning apparatus of run-in index, by the slow pushing syringe of syringe pump, solution is extruded.At first the PVA/Au-Ag spinning solution is placed in the syringe of 10 mL, the parameter adjustment of syringe pump is that the discharge rate of spinning solution is 0.3 mL/h.Spinning voltage is 12 kV, and the distance between spinning mouth and receiving screen is 10 cm, and the spinning time is 2 h, obtains the PVA/Au-Ag nanofiber, and the content of Au-Ag is 4 * 10
-5Mol/g, Au:Ag is respectively 0:1,1:1,2:1,3:1 and 1:0.
Referring to accompanying drawing 3, it is the ultraviolet-visible absorption spectroscopy comparison diagram of the contained Au that provides of the present embodiment alloy nano particle different with the Ag ratio; In figure, curve a, b, c, d, e, f, g represent respectively Ag, Au
1Ag
3, Au
1Ag
2Au
1Ag
1, Au
2Ag
1, Au
3Ag
1With the Au nano particle.As seen from Figure 3, all Au-Ag alloy nano particles only show a surface plasma resonance absorbtion peak, between Au and Ag, and along with the increase of Au content, surface plasma resonance peak (SPR) red shift gradually of Au-Ag alloy nano particle.
Referring to accompanying drawing 4, it is the TEM photo comparison diagram of the PVA/Au-Ag nanofiber of the contained Au that provides of the present embodiment alloy nano particle different with the Ag ratio; In figure, photo a, b, c, d, e, f, g correspondence respectively comprise Ag, Au
1Ag
3, Au
1Ag
2Au
1Ag
1, Au
2Ag
1, Au
3Ag
1PVA nanofiber with the Au nano particle.Can obviously find out in the TEM photo: the size of the Au-Ag nano particle on single fiber and distribution, by electrostatic spinning, large variation does not occur in the pattern of particle and particle diameter.As calculated, in fiber, the concentration of nano particle is about 4 * 10
-5Molg
-1.
Referring to accompanying drawing 5, it is the surface plasmon resonance absorption wavelength comparison diagram of the contained Au that provides of the present embodiment PVA/Au-Ag nanofiber different with the Ag ratio; In figure, curve a, b, c, d, e, f, g corresponding expression respectively comprise Ag, Au
1Ag
3, Au
1Ag
2Au
1Ag
1, Au
2Ag
1, Au
3Ag
1PVA nanofiber with the Au nano particle.Compare with the ultraviolet of Au-Ag nano particle in solution, the peak shape broadening of Au-Ag nano particle in the PVA fiber, there is a little red shift the position at surface plasma body resonant vibration peak, and this is because the residing media environment difference of Au-Ag nano particle causes.
Referring to accompanying drawing 6, it is to adopt three kinds of molecules that are usually used in the Raman test as analyte, be respectively mercaptobenzoic acid (4-MBA), pyridine and benzenethiol, the PVA/Au-Ag nanofiber that the present embodiment provides is tested as the performance of surface-enhanced Raman (SERS) substrate.In Fig. 7, each figure corresponds to respectively: 4-MBA (A1, A2), pyridine (B1, B2) and benzenethiol (C1, C2) at 514.5 nm (A1, B1, C1) the SERS collection of illustrative plates under and 632.8 nm (A2, B2, C2) excitation wavelength, in figure, curve a, b, c, d, e, f, g represent respectively to comprise Ag, Au
1Ag
3, Au
1Ag
2, Au
1Ag
1, Au
2Ag
1, Au
3Ag
1PVA nanofiber with the Au nano particle.Can be found out by each SERS figure in Fig. 6, the SERS signal that obtains on all PVA/Au-Ag nanofibers all is better than the PVA/Au nanofiber far away, some also strong than PVA/Ag even, produce the former of this phenomenon because: the surface plasma body resonant vibration absorbing wavelength of Au-Ag alloy nano particle is with to excite light wavelength relevant with the matching degree of the UV absorption wavelength of analyte molecule.Can find out from the SERS collection of illustrative plates of three kinds of molecules, the ratio of the Au/Ag of SERS intensity-dependent in the Au-Ag particle, and be not single increase or reduce, along with the increase of Au content, first increases and then decreases, reach the strongest SERS intensity when Au:Ag is 1:2 or 1:3.
Press embodiment 2 technical schemes, add simultaneously the HAuCl of configuration in mass concentration is 1% PVA solution
4(2 mmol, 3 mL) and AgNO
3(2 mmol, 9 mL), then be heated to boiling, by mass fraction, add the sodium citrate solution that accounts for reaction system 0.3 %, continue boiling 2 h, namely obtain gold-silver alloy nanoparticles colloidal solution, the mol ratio of the synthetic Au of reduction and Ag is the alloy nano particle of 1:3, and meter is made Au
1Ag
3.
Au with preparation
1Ag
3Alloy nano particle colloidal solution under the rotating speed of 6000 rpm centrifugal three times, each 25 minutes, after removing unreacted metal salt solution; Add the PVA solution of appropriate 10 wt% fully to mix, obtain PVA/Au
1Ag
3PVA concentration in solution is controlled to be 8 wt%, Au
1Ag
3The spinning solution that is 4 mmol is used for electrostatic spinning.
Adopt the electrostatic spinning apparatus of run-in index, by the slow pushing syringe of syringe pump, solution is extruded.At first with PVA/ Au
1Ag
3Spinning solution is placed in the syringe of 10 mL, and the parameter adjustment of syringe pump is that the discharge rate of spinning solution is 0.3 mL/h.Spinning voltage is 12 kV, and the distance between spinning mouth and receiving screen is 10 cm, obtains PVA/Au
1Ag
3Nanofiber, Au
1Ag
3Content be 4 * 10
-5Mol/g.
Press the technical scheme of the present embodiment, prepare respectively PVA/Au
1Ag
3PVA concentration in solution in solution is controlled to be 8 wt%, Au
1Ag
3The spinning solution that is respectively 1,2,3 and 5 mmol is used for electrostatic spinning, obtains Au
1Ag
3Content is respectively 1 * 10
-5Mol/g, 2 * 10
-5Mol/g, 3 * 10
-5Mol/g and 5 * 10
-5The PVA/Au of mol/g
1Ag
3Nanofiber.
Referring to accompanying drawing 7, it in the PVA of the present embodiment preparation/Au-Ag nanofiber during different Au-Ag alloy nano particle content to the SERS collection of illustrative plates of mercaptobenzoic acid (4-MBA), curve S 1～S5 represents respectively different Au-Ag alloy nano particle umbers, the content that is the Au-Ag alloy nano particle from S1～S5 is respectively 1 mmol, 2 mmol, 3 mmol, 4 mmol and 5 mmol.In Fig. 7, figure a is that excitation wavelength is 514 nm, the Au that a series of content increase progressively
1Ag
3PVA/Au
1Ag
3The surface Raman enhancement spectrogram of nano-fiber film to 4-MBA, can be seen by figure a, along with Au in nano-fiber film
1Ag
3With the increase of the molar ratio of PVA, the Au on the fiber membrane unit are
1Ag
3The surface density of nano particle, and the PVA/Au that is adsorbed on unit are
1Ag
3The quantity of the 4-MBA molecule on nano-fiber film all increases simultaneously, and on SERS, the intensity of Raman peaks increases gradually.In Fig. 7, that figure b represents is 1586 cm
-1With 1079 cm
-1Raman peaks intensity from the change curve of S1～S5, can be seen by figure b, from S3, the efficiency of the increase of Raman peaks intensity starts to diminish.As the Au in fruit fiber
1Ag
3Nano particle very little, can't form " hot-zone ", so the intensity of S1 is very little, when the nano particle number increases, the part nano particle starts to form dimer or gathering, and the interaction between particle and particle is the very large effect of performance in electric field strengthens, and Raman peaks intensity significantly increases.But if the nano particle number continues to increase, the amplitude of increase starts to diminish.
Press the technical scheme of embodiment 2, preparation PVA concentration is 8 wt%, Au
1Ag
3, for the spinning solution of 4mmol, be used for electrostatic spinning and preparation drop-casting casting film.
Adopt the electrostatic spinning apparatus of run-in index, obtain Au
1Ag
3Be 4 * 10
-5The PVA/Au of mol/g
1Ag
3Nanofiber.
Comparative Examples: the PVA/ Au that makes by the present embodiment
1Ag
3Spinning solution spreads upon on the cover glass of 18 mm * 18 mm, is placed in drying cupboard, after solvent evaporates, on the cover glass surface, forms layer of Au
1Ag
3Be 4 * 10
-5The PVA/Au of mol/g
1Ag
3Film.
In order to estimate the SERS performance of the prepared PVA/Au-Ag nano-fiber film of the present invention, the comparison of SERS performance is carried out in the substrate of itself and drop-casting method preparation.Referring to accompanying drawing 8, it is the PVA/Au of the present embodiment preparation
1Ag
3The comparison diagram of the SERS intensity of nanofiber and drop-cast film (Comparative Examples).In Fig. 8, curve A is the PVA/Au that method of electrostatic spinning obtains
1Ag
3Nanofiber is as the SERS substrate, and curve B is identical Au
1Ag
3/ PVA spinning solution directly drops on 18 clean mm * 18 mm cover glasses, at room temperature, becomes the Comparative Examples of film after solvent evaporates is complete.From to 2 mM 4-MBA solution, at two kinds of suprabasil SERS collection of illustrative plates, can obviously finding out, the nanofiber that the electrostatic spinning that the present embodiment provides obtains has higher sensitivity than drop-cast film.
Claims (2)
1. the preparation method of a surface-enhanced Raman scattering activity substrate, is characterized in that comprising the steps:
(1) adding molar concentration in mass concentration is 0.5～2% polyvinyl alcohol water solution is the HAuCl of 0.1～5 mmol/L
4Solution and molar concentration are the AgNO of 0.1～5 mmol/L
3Solution, by mole densimeter, Au:Ag is 1:2～1:3, is heated to boiling; Adding mass concentration in reaction system is 0.2～0.5% natrium citricum, and under the boiling condition, fully reaction, obtain Au-Ag alloy nano particle colloidal solution;
The Au-Ag alloy nano particle colloidal solution eccentric cleaning that (2) will prepare, add polyvinyl alcohol water solution, controlling the polyvinyl alcohol mass concentration is 8～10%, the molar concentration of Au-Ag alloy nano particle is 0.01～0.1 mol/L, fully mix under stirring condition, obtain polyvinyl alcohol/Au-Ag alloy nano particle spinning solution;
(3) adopt the electrostatic spinning apparatus of run-in index, spinning voltage is 8～14 kV, and the distance between spinning mouth and receiving screen is 8～15 cm, obtains a kind of surface-enhanced Raman scattering activity substrate.
2. the surface-enhanced Raman scattering activity base material that obtains by claim 1 preparation method is characterized in that: it is polyvinyl alcohol/Au-Ag alloy nano particle composite nano fiber, and by mole densimeter, the content of Au-Ag alloy nano particle is 2 * 10
-4～2 * 10
-2Mol/g, in molar ratio, Au:Ag is 1:2～1:3.
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