CN104931733A - Shell isolation silver nanoparticle tip preparation method - Google Patents
Shell isolation silver nanoparticle tip preparation method Download PDFInfo
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- CN104931733A CN104931733A CN201510340505.7A CN201510340505A CN104931733A CN 104931733 A CN104931733 A CN 104931733A CN 201510340505 A CN201510340505 A CN 201510340505A CN 104931733 A CN104931733 A CN 104931733A
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Abstract
The invention discloses a shell isolation silver nanoparticle tip preparation method. The method comprises the steps that 1) an electrochemical etching method is used to prepare a scanning probe microscope type silver nanoparticle tip; and 2) the surface of the silver nanoparticle tip is coated through silicon dioxide to acquire a uniform and dense silicon dioxide shell, wherein the thickness of the shell is between 1 and 10nm. According to the invention, the prepared shell isolation silver nanoparticle tip is protected by the dense shell; the performance of the silver nanoparticle tip is not affected by external environment; and the shell isolation silver nanoparticle tip can be stored for a long time and repeatedly used, and maintains a good optical performance.
Description
Technical field
The present invention relates to a kind of preparation method of shell isolated silver nanoparticle needle point, especially relate to the silver nanoparticle needle point coated with silica method being applicable to scanning probe microscopy and Tip-Enhanced Raman Spectroscopy.
Background technology
Along with science and technology develop rapidly along with, the synthesis Study on Preparation Technology of metal nano material is more deep.Silver nano material, because its optical dispersion effect, has high optical activity at visible light wave range, is subject to the extensive concern of Surface Science circle.For example in Tip-Enhanced Raman Spectroscopy, because silver nanoparticle needle point is under laser irradiates, excites surface phasmon, caused the enhancing of near field electromagnetic field strength, be exaggerated the optical signalling of surface adsorbed molecules.But acupuncture needle point has defect equally.Because silver nano material is comparatively active, after preparation, just easily receive the pollution of oxygen and sulfide in atmosphere, form one deck oxide/sulfurized layer on surface.The silver nanoparticle needle point of conventional preparation is because the impact of oxidation stain, and enhancing ability is along with sharply declining standing time, and serviceable life was limited within a couple of days, and be not suitable for solution mutually in experiment because the influence factors such as electricity contact, molecule contacts can be there is.In biologic applications, because the precipitation of silver-colored body or silver ion, silver nano material has toxicity to biological cell.In addition, traditional silver nanoparticle needle point, can because localized electromagnetic field strengthens the high temperature brought when carrying out Tip-Enhanced Raman Spectroscopy experiment, and make tip end generation deformation, and then just lose activity after single experiment, recycling rate of waterused is extremely low.In existing document, use ~ 3nm alumina layer carries out coated to silver-colored needle surface, but obtains final pattern heterogeneity, comparatively coarse.(C.A.Barrios, A.V.Malkovskiy, A.M.Kisliuk; A.P.Sokolov, M.D.Foster, J.Phys.Chem.C 113; 8158) so urgent need one can be protected silver nanoparticle needle surface, but the method for its surface topography and optical property is not affected.2010 time, Tanaka group's teach problem group uses inert material shell coated golden nanometer particle synthetic method, can available protecting metal Nano structure kernel by the pollution of extraneous probe molecule.(Li, J.F.; Huang, Y.F.; Ding, Y.; Yang, Z.L.; Li, S.B.; Zhou, X.S.; Fan, F.R.; Zhang, W.; Zhou, Z.Y.; WuDe, Y.; Ren, B.; Wang, Z.L.; Tian; Z.Q.; Nature2010; 464; 392.) in this invention; we use the silica shell method for coating with controllable thickness; prepare shell isolated silver nanoparticle needle point; be intended to protection silver nanoparticle needle point be not affected by the external environment; while obtaining longer serviceable life, there is stronger optical activity, and protect the localized hyperthermia of silver-colored tip end not by optical excitation in experimentation to affect; can reuse depositing in process, be particularly useful for the research in solution phase and living things system.
Summary of the invention
Object of the present invention is intended to for the deficiency in traditional preparation methods, provides a kind of under the prerequisite not affecting silver nanoparticle needle surface pattern and subsequent applications, with the preparation method on silica shell coated with silver nanometer pinpoint surface.
Described use shell isolated silver nanoparticle needle point preparation method draws together following step:
A preparation method for shell isolated silver nanoparticle needle point, is characterized in that comprising the following steps:
1). use electrochemical etching method, prepare scanning probe microscopy type silver nanoparticle needle point;
2). carry out coated with silicon dioxide to silver nanoparticle needle surface, obtain densification, homogeneous silica shell, shell thickness is at 1 ~ 10nm:
Be that 0-0.6mM sodium citrate mixes with 0-1.0mM ascorbic acid solution by ultimate density, immerse silver nanoparticle needle point, and add the silane coupler solution that ultimate density is respectively 0.01-0.5mM, the sodium borohydride solution of 4-8mM and the sodium silicate of 0.02-0.8%wt. or teos solution, and adjust ph is 9.2 ~ 9.7; After stirring, move in 100 DEG C of water-baths, take out needle point after 0.2-1h, carry out drip washing with ultrapure water, complete preparation.
Wherein, step 2) be preferably that 0.4-0.6mM sodium citrate mixes with 0.6-1.0mM ascorbic acid solution by ultimate density.
Wherein, step 1) method for optimizing is as follows: the configuration of electrochemical etching method etching liquid: solution composition is perchloric acid: methyl alcohol volume ratio=1-2:1-2, platinum circle is as to electrode, cut-off footpath is the filamentary silver of 0.1-0.5mm again, makes filamentary silver bottommost concordant with the plane that platinum circle is formed, control voltage, make current stabilization at 0.01-0.1A, shifted out by needle point rapidly after etching terminates, rinse surface with absolute ethyl alcohol immediately, preparation process terminates.
Wherein, filamentary silver length is preferably 1-5cm.
Wherein, step 2) described in silane coupling agent comprise at least one in (3-aminopropyl) triethoxysilane, Methoxyamino silane, ethoxy hydrosulphonyl silane, methoxyl hydrosulphonyl silane.
Wherein, step 2) adopt acid to regulate pH, described acid comprises at least one in sulfuric acid, hydrochloric acid, carbonic acid, phosphoric acid.
Wherein, step 2) in, be that 0.5mM sodium citrate mixes with 0.8mM ascorbic acid solution by ultimate density, immerse silver nanoparticle needle point, and add ultimate density and be respectively 0.02mM, (3-aminopropyl) triethoxysilane solution, sodium borohydride solution and sodium silicate solution of 5.5mM and 0.054%wt..And by sulfuric acid solution adjust ph 9.2 ~ 9.7; After stirring, move in 100 DEG C of water-baths, take out needle point after 0.5h, carry out drip washing with ultrapure water, preparation completes.
By step 1) in the silver nanoparticle needle point of electrochemical etching, carry out Tip-Enhanced Raman Spectroscopy experiment.Substrate used is the golden monocrystalline being assembled with p-aminophenyl thiophenol molecular layer, and assembling process is be that the golden monocrystalline of (111) index is immersed in 30min ~ 2h in 1mM p-aminophenyl thiophenol solution by crystal plane structure, then uses ethanol rinse dry, stand-by.The instrument used is the pinpoint enhanced Raman instrument based on scanning probe microscopy type, and be configured as setting sun formula, LASER Light Source 633nm, power 0.1mW, acquisition time is 1s.When can see that silver nanoparticle needle point carries out Tip-Enhanced Raman Spectroscopy, p-aminophenyl thiophenol, under the catalysis of silver, generates coupled product '-dimercaprol azobenzene, and the spectral intensity of the latter is more better than the former, makes the analysis of p-aminophenyl thiophenol receive larger interference.
Using step 3) the shell isolated silver nanoparticle needle point that obtains carries out Tip-Enhanced Raman Spectroscopy experiment.
By step 3) the middle shell isolated silver nanoparticle needle point with 1 ~ 2nm silica shell layer thickness synthesized, carries out Tip-Enhanced Raman Spectroscopy experiment.Substrate used is the golden monocrystalline being assembled with p-aminophenyl thiophenol molecular layer, and assembling process is be that the golden monocrystalline of (111) index is immersed in 30min ~ 2h in 1mM p-aminophenyl thiophenol solution by crystal plane structure, then uses ethanol rinse dry, stand-by.The instrument used is the pinpoint enhanced Raman instrument based on scanning probe microscopy type, and be configured as setting sun formula, LASER Light Source 633nm, power 0.3mW, acquisition time is 10s.Can see if when carrying out Tip-Enhanced Raman Spectroscopy with shell isolated silver nanoparticle needle point, the spectral signature of p-aminophenyl thiophenol is obvious, does not have because become other molecules with the role transformation of acupuncture needle point.Shell isolated silver nanoparticle needle point is shown can effectively to avoid the interaction of impurity molecule and acupuncture needle point and the interference caused, even if power is increased to three times that use in the needle point experiment of not coated shell relatively, and by time lengthening 10 times, p-aminophenyl thiophenol still can not be caused to the chemical transformation of '-dimercaprol azobenzene.
Compared with traditional method, the present invention has following outstanding advantage and technique effect:
1) preparation-obtained shell isolated silver nanoparticle needle point in the present invention, when doing scanning tunnel microscope and Tip-Enhanced Raman Spectroscopy experiment, the pollution of solution and the pollution of adsorbing species can not be there is, so be specially adapted to solution system and biological cell system, and can alleviate because carrying out in optic test, localized electromagnetic field enhancing causes the high temperature in tip end generation and makes needle point thawing, deformation, and the optical property inactivation brought;
2) the shell isolated silver nanoparticle needle point prepared by the present invention is because there is the protection of fine and close shell, and silver nanoparticle needle point performance is not affected by the external environment, can long storage time and reusing, and keeps good optical property;
3) preparation method of the shell isolated silver nanoparticle needle point used in the present invention, the time is short, simple to operate, once can carry out the coated of up to a hundred even thousands of silver nanoparticle needle points, is applicable to producing preparation in enormous quantities, and can deposits for a long time, in a large number.
Accompanying drawing explanation
Fig. 1 is step 1) in the scanning electron microscope (SEM) photograph of prepared silver nanoparticle needle point, in FIG, scale is 10 μm.
Fig. 2 is step 3) in prepared shell isolated silver nanoparticle needle point transmission electron microscope picture, in fig. 2, scale is 100nm.
Fig. 3 is step 5) in use the silver nanoparticle needle point of non-coated silica shell carry out p-aminophenyl thiophenol Tip-Enhanced Raman Spectroscopy experiment.
Fig. 4 is step 6) the middle Tip-Enhanced Raman Spectroscopy experiment using shell isolated silver nanoparticle needle point to carry out p-aminophenyl thiophenol.
Embodiment
Following examples will the invention will be further described by reference to the accompanying drawings.
Embodiment 1: in electrochemical method etching prepare acupuncture needle point concrete steps be:
The required solution of configuration etching, consists of by volume=the perchloric acid of 1:2 mixing: methanol solution is to electrode with platinum circle, get that length is ~ 2cm, diameter is the filamentary silver of 0.25mm, make filamentary silver bottommost concordant with platinum circle, modulation voltage, current stabilization is made to control at 0.06A, when electric current reduces to 0, after namely etching terminates, shift out needle point rapidly, surface is rinsed immediately with absolute ethyl alcohol, preparation process terminates, then obtained silver nanoparticle needle point is carried out scanning electron microscope shooting, obtains Fig. 1.
Embodiment 2: the preparation of shell isolated silver nanoparticle needle point:
Be that 0.5mM sodium citrate mixes with 0.8mM ascorbic acid solution by ultimate density, silver nanoparticle needle point slowly enters in solution, and add ultimate density and be respectively 0.02mM, (3-aminopropyl) triethoxysilane solution, sodium borohydride solution and sodium silicate solution of 5.5mM and 0.054%wt..Stir with magnetite, and by sulfuric acid solution adjust ph 9.2 ~ 9.7.After stirring, move in 100 DEG C of water-baths, take out needle point after 0.5h, carry out drip washing with ultrapure water, preparation completes.Again by the shell isolated silver nanoparticle needle point shooting transmission electron microscope of preparation, obtain Fig. 2.
Embodiment 3: use step 1) the non-encapsulated silver nanoparticle needle point that obtains carries out Tip-Enhanced Raman Spectroscopy experiment.
By step 1) in the silver nanoparticle needle point of electrochemical etching, carry out Tip-Enhanced Raman Spectroscopy experiment.Substrate used is the golden monocrystalline being assembled with p-aminophenyl thiophenol molecular layer, and assembling process is be that the golden monocrystalline of (111) index is immersed in 30min ~ 2h in 1mM p-aminophenyl thiophenol solution by crystal plane structure, then with stand-by after ethanol rinse.Use the pinpoint enhanced Raman instrument based on scanning probe microscopy type, and carry out laser incidence with setting sun formula, LASER Light Source 633nm, power 0.1mW, acquisition time is 1s.Obtain spectrogram 3 when using silver nanoparticle needle point to carry out Tip-Enhanced Raman Spectroscopy, p-aminophenyl thiophenol has been catalytically converted into '-dimercaprol azobenzene at silver.
Embodiment 4: use step 3) the shell isolated silver nanoparticle needle point that obtains carries out Tip-Enhanced Raman Spectroscopy experiment.By step 3) in the shell isolated silver nanoparticle needle point for preparing, carry out Tip-Enhanced Raman Spectroscopy experiment.Substrate used is the golden monocrystalline being assembled with p-aminophenyl thiophenol molecular layer, and assembling process is be that the golden monocrystalline of (111) index is immersed in 30min ~ 2h in 1mM p-aminophenyl thiophenol solution by crystal plane structure, then with stand-by after ethanol rinse.Use the pinpoint enhanced Raman instrument based on scanning probe microscopy type, and carry out laser incidence with setting sun formula, LASER Light Source 633nm, power 0.3mW, acquisition time is 10s.When using shell isolated silver nanoparticle needle point to carry out Tip-Enhanced Raman Spectroscopy, can not there is catalysis in p-aminophenyl thiophenol, obtain spectrogram 4.
Claims (7)
1. a preparation method for shell isolated silver nanoparticle needle point, is characterized in that comprising the following steps:
1). use electrochemical etching method, prepare scanning probe microscopy type silver nanoparticle needle point;
2). carry out coated with silicon dioxide to silver nanoparticle needle surface, obtain densification, homogeneous silica shell, shell thickness is at 1 ~ 10nm:
Be that 0-0.6mM sodium citrate mixes with 0-1.0mM ascorbic acid solution by ultimate density, immerse silver nanoparticle needle point, and add the silane coupler solution that ultimate density is respectively 0.01-0.5mM, the sodium borohydride solution of 4-8mM and the sodium silicate of 0.02-0.8%wt. or teos solution, and adjust ph is 9.2 ~ 9.7; After stirring, move in 100 DEG C of water-baths, take out needle point after 0.2-1h, carry out drip washing with ultrapure water, complete preparation.
2. the preparation method of a kind of shell isolated silver nanoparticle needle point as claimed in claim 1, is characterized in that: step 2) be that 0.4-0.6mM sodium citrate mixes with 0.6-1.0mM ascorbic acid solution by ultimate density.
3. the preparation method of a kind of shell isolated silver nanoparticle needle point as claimed in claim 1, it is characterized in that: step 1) configuration of electrochemical etching method etching liquid: solution composition is perchloric acid: methyl alcohol volume ratio=1-2:1-2, platinum circle is as to electrode, cut-off footpath is the filamentary silver of 0.1-0.5mm again, make filamentary silver bottommost concordant with the plane that platinum circle is formed, control voltage, make current stabilization at 0.01-0.1A, rapidly needle point is shifted out after etching terminates, rinse surface with absolute ethyl alcohol immediately, preparation process terminates.
4. the preparation method of a kind of shell isolated silver nanoparticle needle point as claimed in claim 3, is characterized in that: filamentary silver length is 1-5cm.
5. the preparation method of a kind of shell isolated silver nanoparticle needle point as claimed in claim 1, is characterized in that: step 2) described in silane coupling agent comprise at least one in (3-aminopropyl) triethoxysilane, Methoxyamino silane, ethoxy hydrosulphonyl silane, methoxyl hydrosulphonyl silane.
6. the preparation method of a kind of shell isolated silver nanoparticle needle point as claimed in claim 1, is characterized in that: step 2) adopt acid to regulate pH, described acid comprises at least one in sulfuric acid, hydrochloric acid, carbonic acid, phosphoric acid.
7. the preparation method of a kind of shell isolated silver nanoparticle needle point as claimed in claim 1, it is characterized in that: step 2) in, be that 0.5mM sodium citrate mixes with 0.8mM ascorbic acid solution by ultimate density, immerse silver nanoparticle needle point, and add ultimate density and be respectively 0.02mM, (3-aminopropyl) triethoxysilane solution, sodium borohydride solution and sodium silicate solution of 5.5mM and 0.054%wt..And by sulfuric acid solution adjust ph 9.2 ~ 9.7; After stirring, move in 100 DEG C of water-baths, take out needle point after 0.5h, carry out drip washing with ultrapure water, preparation completes.
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| CN111239211A (en) * | 2019-11-20 | 2020-06-05 | 浙江工业大学 | Electrochemical preparation method of silver wire sensing electrode |
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| CN111239211A (en) * | 2019-11-20 | 2020-06-05 | 浙江工业大学 | Electrochemical preparation method of silver wire sensing electrode |
| CN111239211B (en) * | 2019-11-20 | 2022-05-17 | 浙江工业大学 | Electrochemical preparation method of silver wire sensing electrode |
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