CN104198465A - Method for synthesizing silver substrate and application of method - Google Patents
Method for synthesizing silver substrate and application of method Download PDFInfo
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- CN104198465A CN104198465A CN201410512298.4A CN201410512298A CN104198465A CN 104198465 A CN104198465 A CN 104198465A CN 201410512298 A CN201410512298 A CN 201410512298A CN 104198465 A CN104198465 A CN 104198465A
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- money base
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Abstract
The invention discloses a method for synthesizing a silver substrate and application of the method, and relates to the technical field of research of surface phenomena related to adsorption molecules, particularly a synthesizing technology for a metallic nano material substrate used as a probe molecule in SERS detection. The method comprises the following steps: adopting a hydro-thermal synthesis method, using silver nitrate as a silver source, using urea as an ammonia source, using formaldehyde as a reducer, changing the pH value of a solution through the urea, under the hydro-thermal condition, gradually reducing silver, and then preparing the silver substrate, wherein the silver substrate can be used as the substrate for researching surface enhanced raman scattering (SERS). The method is simple, convenient and fast, the used raw materials are relatively cheap, the synthesized product is stable in surface and convenient to store, and the method can be directly used for product representation and SERS detection.
Description
Technical field
The present invention relates to the studying technological domain of the surface phenomena relevant to adsorbing molecule, particularly in SERS detects as the synthetic technology of the metal nano material substrate of probe molecule.
Background technology
Surface enhanced raman spectroscopy (SERS) technology is few and harmless to the testing requirement amount of sample, highly sensitive, the surface phenomena that main research is relevant to absorption molecule, adsorbs the surface reaction of the surface orientation of molecule, the kind of determining absorption molecule, research absorption molecule etc. as measured.The fast development of SERS has made it in an increasingly wide range of applications at medicine, material, food, sensor field.
Under normal circumstances, the most important condition that SERS effect can produce is smoothly exactly that probe molecule will be tried one's best close to the surface of substrate by suction-operated, this just requires substrate to have specific structure, and is commonly used to mainly comprise metal as the material of SERS substrate semiconductor nano material etc.Metal nano material mainly contains Au, Ag, Cu, Pt and Pd etc., and semiconductor nano material mainly contains CdS, CuO, ZnO, TiO
2and Fe
2o
3deng.At present, mainly contain the effect that SERS is probed in substrate that three kinds of directions obtain metal nano material: the one, metal electrode strengthens substrate, and the 2nd, metal-sol active substrate, the 3rd, sedimentation is prepared metallic film base.The primary discovery of SERS phenomenon is in the process silver electrode substrate of surface roughening, thereby this is a kind of traditional enhancing substrate.Other metals such as Au, Cu and Pd etc. also can pass through at KCl or H
2sO
4deng the substrate that is enhanced of electrochemical redox in electrolyte solution, then test for SERS.Metal-sol substrate is made up of metal nanoparticle, and except initial classical silver sol, aurosol and copper colloidal sol also have a lot of research reports.The determinative that determines metal-sol SERS enhancement effect degree is the condensation degree of nano particle in colloidal sol, and condensation degree can have the polycoagulant adding to regulate and control.Recently, along with novel preparation method and the use of reductive agent, nano particle in metal-sol is no longer confined to chondritic, and the nanoparticle sol of tetrahedron, octahedron, nucleocapsid structure, the nanostructured such as star-like and flower-shaped starts to be applied to SERS experiment, and has obtained satisfied result.
The preparation of metallic film base mainly realizes by chemogenic deposit or physical deposition, chemogenic deposit refer to chemical reduction method such as application silver mirror reaction etc. by the particle deposition of nano-scale on backing material, the feature of this method is that reaction preparation is simple, and instrument and equipment is simple and easy; Shortcoming is the more difficult control of reaction conditions, and reaction time, temperature of reaction, reagent concentration and substrate surface are all the key factors that affects SERS signal.And current most widely used physical deposition method is under vacuum condition, on the surface of the material such as quartz or silicon chip, evaporation or sputter thickness are the metal film of 2～20 nm, produce degree of roughness and reach the SERS substrate of atomic level thereby the method can effectively reduce the mobility of metallic atom.
Although adopt the method for evaporation or sputtering metal membrane on the surface of the material such as quartz or silicon chip to be widely used, but the film of preparing at present also exists some problems at aspects such as homogeneity, Composition Control, film defects, and this process costs, technological parameter need to optimize.
Summary of the invention
The object of the present invention is to provide a kind of method simple and convenient, use raw material relatively cheap, the synthetic method at the bottom of synthetic product surface-stable, the money base of being convenient to place.
The present invention includes by following steps:
1) pre-treatment of substrate titanium sheet: by titanium sheet with abrasive paper for metallograph sanding and polishing, again successively in ethanol acetone mixed liquor, deionized water for ultrasonic processing, then be placed in aqueous hydrochloric acid solution, heated at constant temperature etching at 85 DEG C, finally cleans titanium sheet good etching in deionized water for ultrasonic;
2) preparation at the bottom of money base: be mixed to form and mix end liquid with silver nitrate and urea, premenstrual titanium sheet after treatment is placed at the bottom of the mixing of 140 DEG C after liquid reaction, then through annealing, preparation obtains Ag/Ti substrate.
The present invention adopts hydrothermal synthesis method, taking silver nitrate as silver-colored source, urea as ammonia source, formaldehyde is as reductive agent, the pH value that changes solution by urea under hydrothermal condition gradually reduction silver so that prepare money base at the bottom of, it can be used as the substrate of research Surface enhanced raman spectroscopy (SERS).The method is simple and convenient, uses raw material relatively cheap, synthetic product surface-stable, is convenient to place, and can be directly used in Characterization of The Products and SERS and detect.
The mixing mol ratio of silver nitrate of the present invention and urea is preferably 1:2.Raman enhancement effect the best in the time that the ratio of silver nitrate and urea is 1:2.
In mixing end liquid, react 24h.Stable at the bottom of the money base that makes of reaction 24h, Nano Silver is large at the suprabasil adhesion of titanium, and this is convenient to further to study the relevant nature at the bottom of money base.
Successively adopt 600,800,1200 object abrasive paper for metallograph to carry out sanding and polishing to titanium sheet.Adopt sand paper from coarse to fine to polish successively after titanium sheet, the oxide of its surface attachment etc. can be worn away, and after fine sandpaper polishing, titanium plate surface has even, tiny groove, the etching processing after being conducive to and the Nano Silver restoring deposition are adsorbed on titanium plate surface.
In described ethanol acetone mixed liquor, the mixed volume of ethanol and acetone is than being 1:1.Adopt the mixed liquor ethanol polarity of this mixing ratio large, acetone polarity is little, and the two equal-volume mixes the organism that is beneficial to Ex-all titanium plate surface.
In described aqueous hydrochloric acid solution, the mixed volume of hydrochloric acid and water is than being 1:1.First consider that hydrochloric acid has oxidisability unlike nitric acid, so adopt hydrochloric acid; Secondly adopt the two equal-volume to mix, carry out etching titanium sheet with the acid of medium tenacity, remove the oxide layer of titanium plate surface and titanium plate surface is carried out to chemical etching.If strong acid, when etching, titanium sheet may be penetrated; If weak acid, titanium plate surface processing undesirable.
The present invention also proposes the application in SERS by the Ag/Ti substrate of preparation.
By Ag/Ti substrate 2 × 10
-5in M R6G solution, soak 1h, after drying, detect for Surface enhanced raman spectroscopy.
Wherein, adopt in via confocal laser Raman spectrometer, light source is the laser instrument of 532 nm, and wave number is 200～1800 cm
-1.
The present invention is adopting after above-mentioned technical scheme, at the bottom of the money base of preparation, the SERS of probe molecule R6G is strengthened to effect fine, to 2 × 10
-5m R6G has obvious Raman enhancement effect, and to 10
-10the SERS signal of M R6G also has certain enhancing.This has illustrated and has utilized after this technology, has greatly increased " focus " of substrate surface, also effectively raises raman scattering intensity, has improved the sensitivity that detects R6G simultaneously.
Brief description of the drawings
Fig. 1 is the volume ratio of silver nitrate/urea in end liquid while being 1:2, the Electronic Speculum figure of prepared Ag/Ti substrate.
Fig. 2 is the volume ratio of silver nitrate/urea in end liquid while being 1:2, prepared Ag/Ti substrate can spectrogram.
Fig. 3 is that the silver nitrate of different blended composition and division in a proportion and porous Ag/Ti substrate prepared by urea are 2 × 10
-5sERS collection of illustrative plates in M R6G solution.
Fig. 4 is that the silver nitrate of different blended composition and division in a proportion and urea are prepared at the bottom of money base at 1653.6cm
-1the raman scattering intensity comparison diagram at place.
Fig. 5 is the SERS collection of illustrative plates in variable concentrations R6G solution at the bottom of the money base making under silver nitrate urea optimal proportion condition.
Embodiment
Embodiment 1:
(1) pre-treatment of substrate titanium sheet: use successively 600,800,1200 object abrasive paper for metallograph sanding and polishings, the ultrasonic processing 20min of difference in the ethanol that is 1:1 in volume ratio successively and the mixed liquor of acetone, deionized water, then put into the aqueous hydrochloric acid solution that volume ratio is 1:1, heated at constant temperature 20min at 85 DEG C in thermostat water bath, finally cleans titanium sheet good etching in deionized water for ultrasonic.
(2) prepare liquid at the bottom of the mixing of silver nitrate urea: first configure respectively 10mM AgNO
3with 10mM urea, then in reactor, add liquid at the bottom of the reaction that contains different silver nitrates and urea ratio, all add 0.10 mL HCHO(formaldehyde), the supplying with deionized water of overall solution volume less than 5 mL in reactor, concrete consumption is in table 1.
table 1:the detailed formula table of liquid at the bottom of the silver nitrate urea mixing of configuration different mol ratio
(3) preparation at the bottom of porous money base: the titanium sheet that step 1 was processed is placed in respectively liquid at the bottom of each mixing, heats 24h at 140 DEG C, is cooled to after room temperature, takes out reactor.
The cooling annealing of deionized water of more reacted semiproduct being put into rapidly to 20 DEG C of left and right, prepares a series of Ag/Ti substrates with this.
(4) Ag/Ti substrate is to 2 × 10
-5the SERS research of M R6G: configuration 2 × 10
-5the R6G solution of M, is immersed in the Ag/Ti substrate preparing in this solution and dries after 1 h.
Raman collection of illustrative plates related in this experiment carries out in via confocal laser Raman spectrometer (Britain), selects the laser instrument of 532 nm as light source, and wave-number range is set as 200～1800 cm
-1.
Through experiment, show that porous Ag/Ti substrate is 2 × 10
-5sERS collection of illustrative plates in M R6G solution, as shown in Figure 3, wherein a to g curve has represented that respectively the mol ratio of silver nitrate and urea is followed successively by 2:3,1:2,2:5,1:3,2:7,1:4,2:9.
Fig. 4 is 1653.6cm for choosing wave number in Fig. 3
-1the comparison diagram that the raman scattering intensity at place is made.
Embodiment 2:
Other method all with embodiment 1 in method, the SERS research that the mol ratio of selecting silver nitrate and urea is the prepared Ag/Ti substrate of 1:2 to variable concentrations R6G: first configure respectively 10
-5m, 10
-7m, 10
-9m, 10
-10m R6G solution soaks 1h respectively by the Ag/Ti substrate making under this condition in above-mentioned solution, draws porous Ag/Ti substrate.
By the Ag/Ti substrate making respectively 10
-5m, 10
-7m, 10
-9m, 10
-10sERS collection of illustrative plates in M R6G solution, as shown in Figure 4.
Can be found out by Fig. 3, Fig. 4, this substrate is to 2 × 10
-5m R6G has obvious Raman enhancement effect, and silver nitrate and urea mol ratio are followed successively by 2:3,1:2,2:5,1:3,2:7,1:4,2:9, corresponding raman scattering intensity first increases and then decreases.Visible, Raman enhancement effect the best in the time that the ratio of silver nitrate and urea is 1:2.
As shown in Figure 5, the Raman of the R6G to variable concentrations at the bottom of the money base of preparing in the time that silver nitrate is optimal proportion with urea mol ratio strengthens different, and along with reducing of R6G concentration, corresponding raman scattering intensity is also reducing, but concentration is low to moderate 10
-10when M, still have certain enhancing signal, this Ag/Ti substrate that shows the porous structure making by returning method has good application prospect aspect SERS.
Claims (8)
1. the method at the bottom of synthetic money base, comprises by following steps:
1) pre-treatment of substrate titanium sheet: by titanium sheet with abrasive paper for metallograph sanding and polishing, again successively in ethanol acetone mixed liquor, deionized water for ultrasonic processing, then be placed in aqueous hydrochloric acid solution, heated at constant temperature etching at 85 DEG C, finally cleans titanium sheet good etching in deionized water for ultrasonic;
2) preparation at the bottom of money base: be mixed to form and mix end liquid with silver nitrate and urea, premenstrual titanium sheet after treatment is placed at the bottom of the mixing of 140 DEG C after liquid reaction, then through annealing, preparation obtains Ag/Ti substrate.
2. the method at the bottom of synthetic money base according to claim 1, the mixing mol ratio that it is characterized in that described silver nitrate and urea is 1:2.
3. the method at the bottom of synthetic money base according to claim 1, is characterized in that reacting 24h mixing in end liquid.
4. the method at the bottom of synthetic money base according to claim 1, is characterized in that successively adopting 600,800,1200 object abrasive paper for metallograph to carry out sanding and polishing to titanium sheet.
5. the method at the bottom of synthetic money base according to claim 1, is characterized in that the mixed volume of ethanol and acetone in described ethanol acetone mixed liquor is than being 1:1.
6. the method at the bottom of synthetic money base according to claim 1, is characterized in that in described aqueous hydrochloric acid solution, the mixed volume of hydrochloric acid and water is than being 1:1.
7. the application of the synthetic Ag/Ti substrate of method in SERS as claimed in claim 1, by Ag/Ti substrate 2 × 10
-5in M R6G solution, soak 1h, after drying, detect for Surface enhanced raman spectroscopy.
8. application according to claim 7, is characterized in that adopting in via confocal laser Raman spectrometer, and light source is the laser instrument of 532 nm, and wave number is 200～1800 cm
-1.
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| CN107328750A (en) * | 2017-06-19 | 2017-11-07 | 吉林大学 | A kind of high activity, surface enhanced Raman scattering substrate of high homogeneity and preparation method thereof |
| CN111122542A (en) * | 2019-12-26 | 2020-05-08 | 厦门大学 | Method for measuring sulfide in water by using surface enhanced Raman spectroscopy |
| CN112481608A (en) * | 2020-11-03 | 2021-03-12 | 江南大学 | Titanium substrate with metal nanoparticles growing on surface in situ and application thereof |
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| CN107328750A (en) * | 2017-06-19 | 2017-11-07 | 吉林大学 | A kind of high activity, surface enhanced Raman scattering substrate of high homogeneity and preparation method thereof |
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| CN111122542A (en) * | 2019-12-26 | 2020-05-08 | 厦门大学 | Method for measuring sulfide in water by using surface enhanced Raman spectroscopy |
| CN112481608A (en) * | 2020-11-03 | 2021-03-12 | 江南大学 | Titanium substrate with metal nanoparticles growing on surface in situ and application thereof |
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Application publication date: 20141210 |