CN103048304A - Preparation method of recyclable surface-enhanced Raman-spectrum active substrate - Google Patents
Preparation method of recyclable surface-enhanced Raman-spectrum active substrate Download PDFInfo
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- CN103048304A CN103048304A CN201210520040XA CN201210520040A CN103048304A CN 103048304 A CN103048304 A CN 103048304A CN 201210520040X A CN201210520040X A CN 201210520040XA CN 201210520040 A CN201210520040 A CN 201210520040A CN 103048304 A CN103048304 A CN 103048304A
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Abstract
The invention belongs to the technical field of laser-Raman spectrum detection appliances and Raman spectrum analysis and detection, and in particular relates to a recyclable surface-enhanced Raman-spectrum active substrate with low cost and good reproducibility, and a preparation method thereof. The substrate is characterized in that a porous titanium dioxide film is loaded on the surface of a carrier base sheet through a dipping and lifting method, and then gold nanoparticles grow on the surface of the titanium dioxide film. The composite substrate has an outstanding surface enhanced effect; and chemical compound molecules absorbed on the surface of gold in a previous Raman experiment can be effectively removed through ultraviolet irradiation, and thus the substrate can be recycled.
Description
Technical field
The invention belongs to laser Raman spectroscopy and detect apparatus and Raman spectrum analysis detection technique field, particularly a kind ofly can be recycled, cost is low, favorable reproducibility be used for surface-enhanced Raman spectrum active substrate and preparation method thereof.
Background technology
Surface enhanced raman spectroscopy (SERS) is a kind of unusual surperficial optical phenomena, refer to when compound absorption or during near some special precious metal surface, its raman scattering cross section strengthens about 4～10 orders of magnitude, the signal to noise ratio (S/N ratio) of Laser Roman spectroscopic analysis of composition is improved greatly, accuracy of detection has produced leap, in some specific system even can reach the detection sensitivity of single molecules level, owing to have high detection sensitivity, the Surface enhanced raman spectroscopy technology is in surface chemistry, analytical chemistry, galvanochemistry, biology and environmental science are widely used.
Yet, surface enhanced Raman scattering effect is to occur under the special experiment condition, the kind of substrate and surface topography etc. there is special requirement, only there is gold present stage, silver, the alkaline metal that three kinds of noble metals of copper and the minority utmost point are of little use is (such as lithium, sodium) has very strong surface enhanced Raman scattering effect, and the use of these noble metals has directly increased the cost that Surface enhanced raman spectroscopy detects, simultaneously these expensive surface-enhanced Raman scattering activity substrates also exist disposable use problem, cause its actual availability to reduce, therefore, the exploitation can be recycled or reused surface enhanced Raman scattering substrate material imperative, Mathias Brust(P. Aldeanueva-Potel, Deng. Anal. Chem., 2009,81,9233.) etc. prepared the Ago-Gel of Ag load, because the Ag nanoparticle surface is coating high-molecular gel, having completely cut off Ag contacts with absorption the direct of molecule, the molecule that adsorbs on the gel surface can pass through the solvent eccysis, realizes recycling of this substrate; Some scholars such as Yao Jianlin (Guo Qinghua, etc. chemical journal, 2011,69,1060. B. Lv, etc. J. Solid State Chem., 2010,183,2968. J. Du, etc. J. Colloid Interf. Sci., 2011,358,54.) Ag or Au nano particle and magnetisable material are built into composite substrate, the mode by the externally-applied magnetic field enrichment reclaims with recycling this composite nanostructure; Or the Au nano particle is coated the SiO of one deck densification
2Shell, isolated Au contacts with absorption the direct of molecule, has obtained a kind of Au@SiO
2The surface enhanced Raman scattering substrate capable of circulation of nucleocapsid structure (D. Li, etc. J. Mater. Chem., 2010,20,3688.); But in the preparation of these substrates, coating thickness control is most important, and (the too thick surface enhanced Raman scattering effect of Au or Ag that causes reduces, too thinly cause and adsorb the direct of molecule and contact), in addition, these substrates may exist also that ultrasonic cleaning is clean, the problems such as pin hole appear in clad.
The present invention is by synthetic TiO
2With the composite substrate of the form of film of Au, utilize TiO
2Photodegradation can remove the compound molecule of Au adsorption, the method need not Au is tightly wrapped up, and has both guaranteed high Raman enhancement effect, has obtained again the characteristic that can be recycled.
Summary of the invention
The object of the invention is to overcome the disposable use deficiency that conventional surface strengthens Raman scattering substrate, design and provide a kind of surface enhanced Raman scattering substrate that can be recycled and preparation method thereof.
Technical solution of the present invention is as follows:
A kind of preparation method of the surface-enhanced Raman scattering activity substrate that can be recycled is characterised in that to comprise the following steps:
1) modification TiO
2The preparation of colloidal sol;
2) carrier substrate area load porous TiO
2Film;
3) the Au nano particle is at porous TiO
2The growth of film surface.
In step 1), the preparation method of described modification TiO2 colloidal sol adopts sol-gel processing: get butyl titanate, absolute ethyl alcohol, glacial acetic acid, diacetone, 90.9% ethanol according to volume ratio 17 ~ 18:69 ~ 71:2.5 ~ 3.5:0.5 ~ 1:10 ~ 13, under the magnetic agitation effect, add successively in the reaction bulb, be mixed with faint yellow transparent TiO
2Colloidal sol then adds Macrogol 2000 according to the ratio that adds 2g in the above-mentioned colloidal sol of every 100mL, is heated to 80 ℃ of stirring and refluxing 1 hour, makes faint yellow transparent poly ethyldiol modified TiO
2Colloidal sol.
In step 2) in the carrier substrate that will be in advance successively cleans up with hydrogen peroxide and sulfuric acid mixture liquid, ethanol, the deionized water of volume ratio 1:4 immersed in the above-mentioned TiO 2 sol 10 ~ 30 minutes, use pulling apparatus that substrate is slowly lifted out colloidal sol, naturally dry, place muffle furnace calcining 3 hours; Because TiO
2Polyglycol in the colloidal sol decomposes to escape in heat treatment process causes TiO
2Film is subject to larger tension force, causes film surface to form porous structure.
The Au nano particle is at porous TiO in step 3)
2The film surface growing method can adopt: with above-mentioned load TiO
2The carrier substrate of film is soaked in and fills 0.5mol/L HAuCl
44H
2In the autoclave of O ethanolic solution, first microwave reaction impelled at TiO in 10 minutes
2Film surface growth Au crystal seed, then the autoclave with sealing places 120 ℃ of baking oven reactions 2 hours, the continued growth of Au crystal seed detects the Au nano particle of required size to surface-enhanced Raman, at last, substrate is taken out, use deionized water rinsing, vacuum drying can obtain surface-enhanced Raman scattering activity base material of the present invention.
Innovative point of the present invention and advantage be in carrier substrate (such as quartz, glass etc.) surface-assembled TiO
2With the form of film composite structure of Au nano particle as the surface-enhanced Raman scattering activity substrate; Utilize TiO
2The photocatalytic activity of film, absorption molecule on the degradable surface-enhanced Raman scattering activity substrate surface, so that substrate is capable of circulation for one or more compound molecules of Raman detection, the method need not the Au nano particle is tightly wrapped up, both guarantee high Raman enhancement effect, obtained again reusable characteristic.
Description of drawings
Fig. 1 is the preparation process synoptic diagram of the surface enhanced Raman scattering substrate of the inventive method preparation;
Fig. 2 is the TiO that is attached on the carrier-pellet of the present invention
2The scanning electron microscope (SEM) photograph of porous membrane;
Fig. 3 is the surface enhanced Raman scattering substrate scanning electron microscope (SEM) photograph of the inventive method preparation;
Fig. 4 is through 12W, and the UV illumination of 254nm is penetrated the methylene blue (1 * 10 after 30 minutes
-5Mol/L) 5 times Surface enhanced raman spectroscopy of circulation;
Fig. 5 is the Raman spectrogram that the surface enhanced Raman scattering substrate of the inventive method preparation is measured the different dyes molecule.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is further described, but should be as restriction protection scope of the present invention.
Embodiment 1
Add successively the butyl titanate of 17.08mL, the absolute ethyl alcohol of 69mL, the glacial acetic acid of 2.9mL in the there-necked flask, and the diacetone of adding 0.5mL, the room temperature lower magnetic force stirred 1 hour, constant pressure funnel slowly splashes into the ethanolic solution (the ethanol/water volume ratio is 10:1) of 11mL 90.9%, gets the faint yellow transparent TiO of 0.5mol/L titanium concentration
2Then colloidal sol add the 2.01g Macrogol 2000 in the above-mentioned colloidal sol, 80 ℃ of stirring and refluxing 1 hour, makes poly ethyldiol modified TiO2 colloidal sol, for subsequent use.
The carrier substrate that present embodiment is chosen is quartz glass plate, successively use hydrogen peroxide/sulfuric acid mixture liquid (volume ratio 1:4), ethanol, washed with de-ionized water piezoid, 100 ℃ of vacuum drying 2 hours according to the preparation synoptic diagram of Fig. 1, are immersed TiO with the quartz glass substrate that cleans up
2Colloidal sol 10 minutes uses czochralski method that substrate is slowly lifted out TiO
2Colloidal sol dries naturally, places muffle furnace slowly to be warming up to 450 ℃ of calcinings 3 hours, and Fig. 2 is the scanning electron microscope (SEM) photograph after the substrate calcining, visible TiO
2Form with porous membrane is coated on the substrate equably, and the aperture is about 1 μ m.
With above-mentioned TiO
2The substrate of film load is soaked in and fills 35mL 0.5mol/L HAuCl
4The autoclave of ethanolic solution in, place microwave reaction 10 minutes, then the baking oven of the reactor of sealing being put into 120 ℃ continues reaction 2 hours, naturally cool to room temperature, substrate is taken out, the water flushing, 80 ℃ of vacuum drying can obtain surface-enhanced Raman scattering activity base material of the present invention.
Fig. 3 is the porous TiO that has assembled the Au nano particle
2The scanning electron microscope (SEM) photograph of film, visible Au nano particle loads on TiO at random
2Film surface, particle diameter is evenly distributed, and average-size is about 20nm, and the Au nano particle is at TiO
2Minute bulk density on the film and particle size can be by regulating HAuCl in the maceration extract
4Concentration controlled.
Embodiment 2
Present embodiment is chosen surface enhanced Raman scattering substrate prepared among the embodiment 1, places 1 * 10
-5Soaked 1 hour in the aqueous solution of methylene blue of mol/L, naturally dry, measure its Surface enhanced raman spectroscopy, test result as shown in Figure 4; Show 10 among Fig. 4
-5The Raman signal of the methylene blue of mol/L on prepared surface enhanced Raman scattering substrate is very obvious, and through 12W, after the UV illumination of 254nm was penetrated 30 minutes, the Raman signal of methylene blue disappeared.Again substrate is soaked in 10
-5After in the methylene blue solution of mol/L, the surface-enhanced Raman signal reproduction so repeats 5 times, shows among Fig. 4 that its surface-enhanced Raman signal is without obvious decay.Experimental result shows that significant cyclic number can reach 20
+
Embodiment 3
Present embodiment is chosen surface enhanced Raman scattering substrate prepared among the embodiment 1, at first places 1 * 10
-5Soak the some time in the aqueous solution of methylene blue of mol/L, measure its Surface enhanced raman spectroscopy.Then at 12 W, irradiation was soaked in 1 * 10 after 30 minutes under the uviol lamp of 254nm
-5In the rose-red aqueous solution of mol/L, measure again its Surface enhanced raman spectroscopy.Again at 12W, irradiation was soaked in 1 * 10 after 30 minutes under the uviol lamp of 254nm at last
-5In the crystal violet aqueous solution of mol/L, measure its Surface enhanced raman spectroscopy, test result as shown in Figure 5; Show among Fig. 5 that through 12W, the ultra violet lamp of 254nm is after 30 minutes, the Raman signal of methylene blue disappears, and this substrate is soaked in 10
-5After in the rose-red solution of mol/L, record rose-red high-quality surface and strengthen Raman signal.Again penetrate through UV illumination, rosy Raman signal disappears.Again this substrate is soaked in 10
-5After in the crystal violet solution of mol/L, obtain the crystal violet high-quality surface and strengthen Raman signal.Test result shows that this substrate can the multiple dye molecule of duplicate measurements.
Claims (6)
1. the preparation method of a surface-enhanced Raman scattering activity substrate that can be recycled is characterized in that comprising the following steps:
1) preparation modification TiO
2Colloidal sol;
2) method that lifts by dipping is at carrier substrate area load porous TiO
2Film;
3) by microwave and hydro-thermal reaction at porous TiO
2Film surface growth Au nano particle.
2. the preparation method of a kind of surface-enhanced Raman scattering activity substrate that can be recycled according to claim 1, it is characterized in that: described carrier substrate is glass sheet, quartz glass plate or titanium dioxide silicon chip.
3. the preparation method of a kind of surface-enhanced Raman scattering activity substrate that can be recycled according to claim 1 is characterized in that: described TiO
2Film is vesicular or the space shape distributes, aperture 0.2 μ m～10 μ m.
4. the preparation method of a kind of surface-enhanced Raman scattering activity substrate that can be recycled according to claim 1, it is characterized in that: in step 1), described modification TiO2 colloidal sol adopts the sol-gel process preparation: get butyl titanate, absolute ethyl alcohol, glacial acetic acid, diacetone, 90.9% ethanol according to volume ratio 17 ~ 18:69 ~ 71:2.5 ~ 3.5:0.5 ~ 1:10 ~ 13, under the magnetic agitation effect, add successively in the reaction bulb, be mixed with faint yellow transparent TiO
2Colloidal sol then adds Macrogol 2000 according to the ratio that adds 2g in the above-mentioned colloidal sol of every 100mL, is heated to 80 ℃ of stirring and refluxing 1 hour, makes faint yellow transparent poly ethyldiol modified TiO
2Colloidal sol.
5. the preparation method of a kind of surface-enhanced Raman scattering activity substrate that can be recycled according to claim 1 is characterized in that: in step 2) in the carrier substrate that will clean up in advance immerse modification TiO
2In the colloidal sol 10 ~ 30 minutes, use pulling apparatus that substrate is slowly lifted out colloidal sol, naturally dry, place muffle furnace to calcine 3 hours; Because TiO
2Polyglycol in the colloidal sol decomposes to escape in heat treatment process causes TiO
2Film is subject to larger tension force, causes film surface to form porous structure.
6. the preparation method of a kind of surface-enhanced Raman scattering activity substrate that can be recycled according to claim 1, it is characterized in that: the Au nano particle is at porous TiO in step 3)
2The film surface growing method is as follows: with supported porous TiO
2The carrier substrate of film is soaked in and fills 0.5mol/L HAuCl
44H
2In the autoclave of O ethanolic solution, first microwave reaction impelled at TiO in 10 minutes
2Film surface growth Au crystal seed, then the autoclave with sealing places 120 ℃ of baking oven reactions 2 hours, the continued growth of Au crystal seed detects the Au nano particle of required size to surface-enhanced Raman, at last, substrate is taken out, use deionized water rinsing, vacuum drying can obtain surface-enhanced Raman scattering activity base material of the present invention.
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|---|---|---|---|---|
| CN105158229A (en) * | 2015-08-13 | 2015-12-16 | 南京理工大学 | Preparation method of high-sensitivity recyclable SERS (surface enhanced Raman spectroscopy) substrate |
| CN105424672A (en) * | 2014-09-04 | 2016-03-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | Non-stoichiometric oxide SERS substrate and preparation method thereof |
| CN105964251A (en) * | 2016-05-16 | 2016-09-28 | 南通大学 | Liquid-phase synthesis method of non-physically adsorbed Au/TiO2 composite nanoparticles and heterojunctions |
| CN106018378A (en) * | 2016-05-11 | 2016-10-12 | 阜阳师范学院 | Method for preparing surface-enhanced Raman scattering active substrate by utilizing sintering technology |
| CN106086880A (en) * | 2016-06-20 | 2016-11-09 | 中国计量大学 | The preparation of a kind of automatically cleaning reusable SERS substrate and application thereof |
| CN106814130A (en) * | 2015-11-30 | 2017-06-09 | 上海交通大学 | It is a kind of for the novel nano chip of Mass Spectrometer Method and its preparation and application |
| CN107091809A (en) * | 2017-06-19 | 2017-08-25 | 江苏师范大学 | A kind of Silver nanorod array surface strengthens the cleaning method of Raman scattering substrate |
| CN107389659A (en) * | 2017-09-21 | 2017-11-24 | 山东师范大学 | A kind of erasable Raman of three-dimensional hypersensitive strengthens active substrate and preparation method |
| CN108330473A (en) * | 2018-03-05 | 2018-07-27 | 中国人民解放军陆军装甲兵学院 | A kind of nano-titanium dioxide film and its preparation method and application |
| CN108802004A (en) * | 2018-06-01 | 2018-11-13 | 徐州医科大学 | The nano titania column array SERS base materials and its preparation method and application of nanowires of gold modification |
| CN108867026A (en) * | 2018-07-19 | 2018-11-23 | 东华大学 | A kind of flexible surface enhancing Raman scattering substrate that can be recycled and its preparation and application |
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| CN108896530A (en) * | 2018-06-29 | 2018-11-27 | 上海交通大学 | A kind of preparation method of Raman spectrum detection substrate |
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| CN110857914A (en) * | 2018-08-23 | 2020-03-03 | 南京理工大学 | Poly (trifluoropropylmethylsiloxane)/silver composite surface enhanced Raman substrate and preparation method thereof |
| CN113388153A (en) * | 2021-04-19 | 2021-09-14 | 华测检测认证集团股份有限公司 | Surface enhanced Raman scattering substrate and manufacturing method thereof |
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| CN108867026A (en) * | 2018-07-19 | 2018-11-23 | 东华大学 | A kind of flexible surface enhancing Raman scattering substrate that can be recycled and its preparation and application |
| CN108867026B (en) * | 2018-07-19 | 2021-05-11 | 东华大学 | Recyclable flexible surface-enhanced Raman scattering substrate and preparation and application thereof |
| CN110857914A (en) * | 2018-08-23 | 2020-03-03 | 南京理工大学 | Poly (trifluoropropylmethylsiloxane)/silver composite surface enhanced Raman substrate and preparation method thereof |
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Application publication date: 20130417 |