CN104525964A - Simple preparing method for regular spherical silver nanometer particles - Google Patents
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Abstract
The invention provides a simple preparing method for regular spherical silver nanometer particles and belongs to the technical field of precious metal nanometer system preparing. The method comprises the following steps that 10, 500 ml of a silver nitrate solution with the molar concentration of 0.53 mmol/L is placed on an electric furnace, and heated to be boiled, and 10 ml of a sodium citrate solution with the molar concentration of 3.4-3.7 mmol/L is added drop by drop so as to prepare silver nanometer particle precursor colloids irregular in shape; 20, 200 ml of the precursor silver colloids are placed into a Petri dish rotating at the rotating speed of 5 r/min, KrF excimer laser with the wave length of 248 nm is utilized for irradiating the colloids, the single pulse energy density is controlled to range from 85 mJ/cm<2> to 150 mJ/cm<2>, and air flow is blown into the surface of liquid in the inverse rotating direction so as to ensure that the colloid solution receives the uniform irradiation intensity. The preparing method can prepare the stable monodispersed silver nanometer particles with the regular spherical surfaces fast and efficiently in a large-scale mode.
Description
Technical field
The invention belongs to noble metal nano system preparation field, relate to a kind of preparation method of spherical silver nano particle of pattern rule.
Background technology
Silver nano-grain, due to its distinctive small-size effect, nanometer size effect and skin effect etc., shows unique performance, as catalysis, electricity/heat transfer, Third-order Nonlinear Optical Properties etc.These distinctive character make silver nano-grain have good application in fields such as biology, catalysis, chemical industry, nano photoelectric device, SERSs.And many characteristics of silver nano-grain and application all closely bound up with its surface topography.The work of numerous researcher is verified, and silver nano-grain surface topography significantly can affect the effect such as electricity, magnetics, catalysis, surface plasma of nano particle.
The most frequently used method the most effectively preparing spherical silver nano particle is mainly following three kinds now:
One, chemical preparation spherical silver nano particle is adopted
Chemical preparation spherical silver nano particle is the main flow preparation method in this field current, silver salt solution (AgNO
3deng) reduced by certain way by reducing agents such as such as natrium citricum, sodium borohydride, hydrogen, and nucleation, growth in the liquid phase, the preparation of the nano particle of various size distribution can be realized by accurately controlling reaction condition.In above-mentioned reducing agent, excessive natrium citricum can prevent the spontaneous coagulation of nano particle, serves as the covering of nano particle while serving as reducing agent.And when using other reducing agent above-mentioned, then need to add in advance high molecular polymer or surfactant to prevent the cohesion of colloidal solid.
Silver nano-grain prepared by the mode of this electronation, it is advantageous that output is large, can realize large-scale production, and its shortcoming is that the pattern of silver nano-grain is difficult to accurate control.Reason is in this approach, and the generation of silver nano-grain can experience two stages---coring and increment.The nucleation process at chemical reaction initial stage determines the final pattern of silver nano-grain, and after nucleation, particle can grow gradually on this basis and become large, and this growth process can not make granule-morphology change.In view of the key affecting Morphologies of Silver Nanoparticles---the molecule that nucleation process relates to is less, dynamics inertia is less, therefore comparatively responsive for external parameter response, obtain single nucleation very difficult, cause being difficult to realize preparation that is single, regular spherical nano particle.In this field, the scientist being representative with Younan Xia, is synthesized by polyalcohol and the method for oxide etch, has prepared the silver nano-grain spherical, the surface topography such as regular hexahedron, regular octahedron is different.Other also achieves very excellent achievement as people such as Peidong Yang.Turkevich., has prepared the monodisperse spherical nano particle of pattern comparatively rule by experiment.But harsh just because of preparation condition, its practicality still can not be accepted by masses.
Two, employing laser, particle beam irradiation prepare spherical silver nano particle.
Utilize laser or energetic particle beam irradiation to prepare spherical nanoparticle and be divided into two kinds of situations:
1, utilize laser or energetic particle beam bombardment Solid Silver target, prepare silver nano-grain solution dispersion system.
This is a kind of physics preparation means of silver nano-grain.Laser and energetic particle beam have very large power density, and the material of target material surface certain depth can be made when bombarding solid target at short notice to produce phase transformation and depart from target body surface.Along with thermal loss forms solid-state nano particle again in liquid phase environment.
Advantage is by this way: nano-Ag particles prepared by (1) has good exterior appearance, be rendered as regular spherical, its principle is pounded the liquid metal of block target, active force between its metallic molecule is a lot of by force with the interaction force between decentralized medium molecule relative to metallic molecule, so under surface tension effects, drop can form the spherical of standard, and keeps this shape invariance in liquid-solid phase transformation subsequently.(2) preparation parameter is easy to accurate control.Key variables involved by this preparation method are energy source power output, and the parameter therefore prepared is easy to control and programming.
But its inferior position is, the productive rate of nano particle is lower, and cost is higher comparatively speaking.
2. utilize laser or energetic particle beam to act on silver salt solution, restore silver nano-grain by photolysis or pyrolysis.
Principle and the chemical reduction method of this preparation method are similar, that the cation of free radical or the free electron silver in silver salt solution produced by high-energy radiation provides reducing agent, thus argent is separated out from solution, control reaction condition and can realize nano particle preparation.
In this preparation method, the surface topography of nano-Ag particles both depended on initial nucleation, also the course of reaction of photolysis or pyrolytic reaction is depended on, hot phase transition process is also mingled with wherein simultaneously, therefore the unstability of parameter is comparatively large, and nano-Ag particles surface topography is difficult to realize uniform regular spherical.
Three, metal vapor condenses preparation method
The method of metal vapor condenses is by being compressed to by metallic vapour in the dispersion circle matter of low temperature, realizes solid nanoparticles preparation by rapid condensation.Because metal nanoparticle is easy to react with water, therefore this process is carried out usually in organic solvent.
This preparation method can extensive preparation scale be nano level Argent grain quickly and efficiently, therefore applies very extensive in, the insensitive industrial circle of size distribution less demanding to granule-morphology.But the process of condensation is difficult to human intervention in addition, the nano-Ag particles quality of preparation is lower, can not present the spherical of height rule.Therefore this mode is difficult to the demand meeting growing high-quality regular spherical nano-Ag particles, thus constrains its application in the industries based on nanotechnology of development.
In sum, the technology of preparing of spherical nano-Ag particles conventional is now difficult to realize the double requirements that a large amount of preparation of the spherical nano-Ag particles of high-quality rule and cost reduce simultaneously, no matter therefore all can not realize applying widely in field of scientific study or commercial field.Spherical nano-Ag particles is the research foundation stone of numerous nanometer technologies such as such as biology, catalysis, surface plasma, surface-enhanced Raman, is also simultaneously nano photoelectric, receives the elementary cell of the technology construction such as micro electronmechanical, artificial micro-intelligence.Therefore, the arrival of nanometer era will produce a large amount of spherical nano-silver demands.For this reason, design a kind of high-quality, high yield, be easy to the regular spherical nano-Ag particles of large-scale production by the prospect of being widely used and potential commercial value.
Summary of the invention
The object of the invention is the preparation of the regular spherical silver nano-grain realizing high yield with a kind of convenient and simple method.
There is the deficiency of the following aspects in the technology of preparing of nowadays conventional spherical silver nano particle: one, for chemical reduction method synthesis mode, the unstability of harshness, the nucleation of reaction condition, the fault-tolerance of preparation condition is low causes product average quality to be difficult to ensure, be all restriction its realize stablizing the outstanding problem that single dispersing prepares spherical silver nano granule.Therefore this method can not really carry out popularizing and then reducing costs realizing commercialization on a large scale.Two, laser, energetic particle beam irradiation prepare liquid phase nano silver colloid, although reduce the complexity of preparation process to a certain extent, preparation output is lower, and cost is high, can not meet the requirement of producing equally on a large scale.Three, for metallic vapour preparation method, although its preparation facilities is simple, productivity ratio is high, and the surface quality of its spherical silver nano granule prepared is too low, is difficult to meet requirements at the higher level.We design a kind of low cost, high-quality, effect and the relatively large liquid phase regular spherical silver nano-grain preparation method of productive rate by experiment for this reason.
A preparation method for regular spherical silver nano-grain, is characterized in that, this preparation method comprises the following steps:
10. prepare the irregular silver nano-grain precursor colloids of pattern.Comprise the following steps:
Glass container is carried out alcohol and ultra-pure water ultrasonic cleaning successively by 101., adds the liquor argenti nitratis ophthalmicus that concentration is (0.51 ~ 0.53) mmol/L, is positioned on electric furnace, is heated to boiling.Be that the sodium citrate solution of 3.4 ~ 3.7mmol/L dropwise joins in solution by concentration, utilize agitator to carry out physical agitation fast simultaneously.The volume ratio of liquor argenti nitratis ophthalmicus and sodium citrate solution controls as 50:1.
After 102. reaction time 20 ~ 30min, close electric furnace, make the precursor colloids of preparation naturally cool to room temperature.
20. utilize presoma elargol to prepare regular spherical silver nano-grain.Comprise the following steps:
The presoma elargol prepared is placed in open glass container by 201., and places it on horizontal rotating table, and setting speed is no more than 10r/min, and the colloidal solution degree of depth is no more than 3cm.
202. are blown into gas by the opposite direction that wireway rotates to open glass container to liquid surface, make liquid unordered flowing in a reservoir.
After 203. ventilation 1min, the PRK that wavelength is 248nm is used to carry out irradiation to forerunner's nanoparticles.It is 200 ~ 450mJ that single pulse energy controls,
After 204. irradiation terminate, stop ventilation, prepare the spherical silver nano-particle colloid of rule.
Further, time prepared by forerunner's silver colloid, the reaction time is 25min.
Further, time prepared by precursor colloids, the liquor argenti nitratis ophthalmicus concentration selected is 0.53mmol/L.
Further, time prepared by precursor colloids, the sodium citrate solution concentration selected is 3.5mmol/L.
Further, time prepared by presoma colloid, high density polyethylene (HDPE) material selected by agitator.
Further, time prepared by precursor colloids, the liquor argenti nitratis ophthalmicus selected and the volume ratio of sodium citrate solution are 50:1.
Further, in step 20, the gas that liquid surface passes in culture dish is N
2or air.
Further, in step 20, the single pulse energy metric density of laser instrument should be 85 ~ 150mJ/cm
2.
According to described method preparation-obtained regular spherical silver nano-grain colloid and powder thereof.
Liquid phase regular spherical silver nano-grain prepared by said method can as the organizational unit of nano-superstructure, by arranging out periodic structure in self-assembling technique or embedding Woelm Alumina, the active substrate of SERS can be used to, build the purposes such as three-dimensional metamaterial.
In preparation process, the size distribution of silver nano-grain depends primarily on chemical preparation condition, and the surface topography of nano particle depends primarily on PRK radiation parameter.In fact, when single laser pulse power is at single pulse energy metric density 85 ~ 150mJ/cm
2, the increase of pulse power can make the surface topography of silver nano-grain more easily be realized by the transformation of irregular polyhedrons to regular spherical.
Beneficial effect:
Compared with prior art, the present invention has following beneficial effect:
1. on pattern, achieve the controllability preparation of regular spherical Nano Silver, experimental implementation is simple, and experiment condition easily meets.The present invention selected present use widely reduction of sodium citrate silver nitrate preparation method as reference group.Figure 1 shows in the simple TEM image using the nano-Ag particles of chemical preparation.2, accompanying drawing show by single pulse energy be the PRK of 350mJ irradiated after nano-Ag particles TEM image.As can be seen from the contrast of two images, the surface topography of silver nano-grain never rules back is regular spherical, achieves the homogenization of the surperficial free degree.The characteristic of this excellence can not only make it meet requirements at the higher level in such as catalysis, antibacterial/antibacterial, SERS, optics, electricity etc., it more can be made for setting up periodic nano-structure on this basis, thus make to realize microeffect and be transformed into possibility to macroeffect.
2., in the optical characteristics of silver nano-grain, regular spherical nano-Ag particles prepared by the method demonstrates excellent plasma resonance characteristic.The present invention selected present use widely reduction of sodium citrate silver nitrate preparation method as reference group.What accompanying drawing 3 showed is the nano-Ag particles colloid UV-visible-near infrared absorption of chemical preparation.What accompanying drawing 4 showed is by single pulse energy be the PRK of 350mJ irradiated after the UV-visible-near infrared absorption of nano-Ag particles.As can be seen from contrast, the regular spherical silver nano-grain absworption peak utilizing the present invention to prepare is narrower, peak shape evenly, accompanying drawing 5 is accompanying drawings 3 and the superposing, so that better its difference of observation of curve in accompanying drawing 4.Excellent surface plasma resonance character can make it obtain good application in fields such as SERS, nano photoelectronic devices, biomolecule detections.
3. safe preparation process, green, easy of integrationization are produced.This preparation method is efficient, simple and have good automation interface, can provide convenient for industrial production.As: the critical operations such as in the preparation process of nano-Ag particles precursor colloids, it is reinforced, stirring, temperature control can realize automation completely; And in the laser irradiation process of precursor colloids, the key parameter such as single pulse energy, repetition rate, umber of pulse of Laser output can be controlled by computer too.And after prepared by colloid, the post processing such as centrifugation, drying work can realize continuous productive process equally, without repeating step in whole preparation process.Therefore, regular spherical silver nano-grain preparation method proposed by the invention possesses and realizes streamline packaging operation prospect.
4. regular spherical silver nano-grain preparation method proposed by the invention simply, rapidly and efficiently, be easy to promote and cost is lower.First, the essence of method described in the present invention is very simple, namely by the irregular silver nano-grain of high energy pulse lasing source irradiation, make it that solid-liquid phase change occur, recycle liquid silver metal molecule and produce strong surface tension relative to the strong interaction force of environmental liquids environmental molecules, strong surface tension makes liquid silver nano-grain present regular spherical.And when liquid Argent grain dissipate energy transfers to solid-state by liquid state, retain spherical regular surfaces, thus obtain the solid-state silver nano-grain of regular spherical.Secondly, this process duration is 10
-8therefore s magnitude is one preparation method fast.Finally, this preparation method can well extend to the other materials outside desilver regular spherical nano particle preparation come up, as cadmium metal, thallium, lead, gold even comprise oxide, semi-conducting material etc.Only need laser or the energetic particle beam radiation of selecting suitable wavelength according to the character of material, and be adjusted to suitable parameter.
Accompanying drawing explanation
Fig. 1: the TEM image of nano-Ag particles prepared by simple use conventional chemical reduction as a comparison in beneficial effect of the present invention.
Fig. 2: utilize the technology of the present invention, by single pulse energy be the PRK of 350mJ irradiated after nano-Ag particles TEM image, be equally also the nano-Ag particles TEM image in embodiment 2.
Fig. 3: the nano-Ag particles colloid UV-visible-near infrared absorption that in beneficial effect of the present invention prepared by simple use conventional chemical reduction as a comparison.
Fig. 4: utilize the technology of the present invention, by single pulse energy be the PRK of 350mJ irradiated after the UV-visible-near infrared absorption of nano-Ag particles, be equally also the abosrption spectrogram in embodiment 2.
The superimposed image of Fig. 5: Fig. 4 and Fig. 3.Wherein spectral line 1 is the spectrum of Fig. 3, and spectral line 2 is the spectrum of Fig. 4.
Fig. 6: the TEM photo of the nano-Ag particles utilizing the embodiment 1 of the technology of the present invention to prepare.
Fig. 7: the UV-visible-near infrared absorption of the nano-Ag particles utilizing the embodiment 1 of the technology of the present invention to prepare.
Fig. 8: the TEM photo of the nano-Ag particles utilizing the embodiment 3 of the technology of the present invention to prepare.
Fig. 9: the UV-visible-near infrared absorption of the nano-Ag particles utilizing the embodiment 3 of the technology of the present invention to prepare.
Figure 10. the TEM photo of the nano-Ag particles utilizing the embodiment 4 of the technology of the present invention to prepare.
Figure 11. the UV-visible-near infrared absorption of the nano-Ag particles utilizing the embodiment 4 of the technology of the present invention to prepare.
The silver nano-grain that Figure 12 utilizes the embodiment 2 of the technology of the present invention to prepare, by SERS (SERS) technology, detects trace crystal violet (CV) molecular signal, the Raman spectrogram obtained.
Detailed description of the invention
Below in conjunction with drawings and Examples, patent of the present invention is described further, but the present invention is not limited to following examples.The KrF excimer pulsed laser of following examples irradiation bomb used to be wavelength be 248nm, laser pulse repetition frequency is 5Hz, and umber of pulse is 6000, and replaceable is other repetition rate or umber of pulse, all can realize.
Embodiment 1
A preparation method for regular spherical silver nano-grain, is characterized in that, this preparation method comprises the following steps:
10. prepare the irregular silver nano-grain precursor colloids of pattern.Comprise the following steps:
The beaker of 700ml is carried out alcohol and ultra-pure water ultrasonic cleaning successively by 101., adds the liquor argenti nitratis ophthalmicus that 500ml concentration is 0.53mmol/L, is positioned on electric furnace, is heated to boiling.Utilize separatory funnel, be that the sodium citrate solution of 3.4mmol/L dropwise joins in solution by 10ml concentration, utilize agitator to carry out physical agitation fast simultaneously.
102. reaction time closed electric furnace, and made the precursor colloids of preparation naturally cool to room temperature after being about 25min.
20. utilize presoma elargol to prepare regular spherical silver nano-grain.Comprise the following steps:
200ml presoma elargol is placed in culture dish by 201., and is placed on horizontal rotating table by culture dish, and setting speed is 5r/min, and the colloidal solution degree of depth is 2cm;
202. are blown into N by the opposite direction that wireway rotates to culture dish to liquid surface
2, gas flow rate is 10cm
3/ s
After 203. ventilation 1min, the PRK that wavelength is 248nm is used to carry out irradiation to forerunner's nanoparticles.Single pulse energy is 300mJ,
After 204. irradiation terminate, stop ventilation, prepare the spherical silver nano-particle colloid of rule.
The TEM image of the spherical nano-silver particle colloid obtained is as shown in Figure 6. and the UV-visible-near infrared absorption of the silver nano-grain colloid obtained is as shown in Figure 7.
Embodiment 2
A preparation method for regular spherical silver nano-grain, is characterized in that, this preparation method comprises the following steps:
10. prepare the irregular silver nano-grain precursor colloids of pattern.Comprise the following steps:
The beaker of 700ml is carried out alcohol and ultra-pure water ultrasonic cleaning successively by 101., adds the liquor argenti nitratis ophthalmicus that 500ml concentration is 0.53mmol/L, is positioned on electric furnace, is heated to boiling.Utilize separatory funnel, be that the sodium citrate solution of 3.4mmol/L dropwise joins in solution by 10ml concentration, utilize agitator to carry out physical agitation fast simultaneously.
102. reaction time closed electric furnace, and made the precursor colloids of preparation naturally cool to room temperature after being about 25min.
20. utilize presoma elargol to prepare regular spherical silver nano-grain.Comprise the following steps:
200ml presoma elargol is placed in culture dish by 201., and is placed on horizontal rotating table by culture dish, and setting speed is 5r/min, and the colloidal solution degree of depth is 2cm;
202. are blown into air by the opposite direction that wireway rotates to culture dish to liquid surface, and gas flow rate is 10cm/s
After 203. ventilation 1min, the PRK that wavelength is 248nm is used to carry out irradiation to forerunner's nanoparticles.Single pulse energy is 350mJ, repetition rate 5Hz, and irradiance pulse quantity is 6000.
After 204. irradiation terminate, continue ventilation 1min, prepare the spherical silver nano-particle colloid of rule.
The TEM image of the spherical nano-silver particle colloid obtained is as shown in Figure 2. and the UV-visible-near infrared absorption of the silver nano-grain colloid obtained is as shown in Figure 4.
Embodiment 3
A preparation method for regular spherical silver nano-grain, is characterized in that, this preparation method comprises the following steps:
10. prepare the irregular silver nano-grain precursor colloids of pattern.Comprise the following steps:
The beaker of 700ml is carried out alcohol and ultra-pure water ultrasonic cleaning successively by 101., adds the liquor argenti nitratis ophthalmicus that 500ml concentration is 0.53mmol/L, is positioned on electric furnace, is heated to boiling.Utilize separatory funnel, be that the sodium citrate solution of 3.4mmol/L dropwise joins in solution by 10ml concentration, utilize agitator to carry out physical agitation fast simultaneously.
102. reaction time closed electric furnace, and made the precursor colloids of preparation naturally cool to room temperature after being about 25min.
20. utilize presoma elargol to prepare regular spherical silver nano-grain.Comprise the following steps:
200ml presoma elargol is placed in culture dish by 201., and is placed on horizontal rotating table by culture dish, and setting speed is 5r/min, and the colloidal solution degree of depth is 2cm;
202. are blown into air by the opposite direction that wireway rotates to culture dish to liquid surface, and gas flow rate is 10cm/s
After 203. ventilation 1min, the PRK that wavelength is 248nm is used to carry out irradiation to forerunner's nanoparticles.Single pulse energy is 400mJ, repetition rate 5Hz, and irradiance pulse quantity is 6000.
After 204. irradiation terminate, continue ventilation 1min, prepare the spherical silver nano-particle colloid of rule.
The TEM image of the spherical nano-silver particle colloid obtained is as shown in Figure 8. and the UV-visible-near infrared absorption of the silver nano-grain colloid obtained is as shown in Figure 9.
Embodiment 4
A preparation method for regular spherical silver nano-grain, is characterized in that, this preparation method comprises the following steps:
10. prepare the irregular silver nano-grain precursor colloids of pattern.Comprise the following steps:
The beaker of 700ml is carried out alcohol and ultra-pure water ultrasonic cleaning successively by 101., adds the liquor argenti nitratis ophthalmicus that 500ml concentration is 0.53mmol/L, is positioned on electric furnace, is heated to boiling.Utilize separatory funnel, be that the sodium citrate solution of 3.4mmol/L dropwise joins in solution by 10ml concentration, utilize agitator to carry out physical agitation fast simultaneously.
102. reaction time closed electric furnace, and made the precursor colloids of preparation naturally cool to room temperature after being about 25min.
20. utilize presoma elargol to prepare regular spherical silver nano-grain.Comprise the following steps:
200ml presoma elargol is placed in culture dish by 201., and is placed on horizontal rotating table by culture dish, and setting speed is 5r/min, and the colloidal solution degree of depth is 2cm;
202. are blown into gas by the opposite direction that wireway rotates to culture dish to liquid surface, and gas flow rate is 10cm/s
After 203. ventilation 1min, the PRK that wavelength is 248nm is used to carry out irradiation to forerunner's nanoparticles.Single pulse energy is 450mJ, repetition rate 5Hz, and irradiance pulse quantity is 6000.
After 204. irradiation terminate, stop ventilation, prepare the spherical silver nano-particle colloid of rule.
The TEM image of the spherical nano-silver particle colloid obtained is as shown in Figure 10. and the UV-visible-near infrared absorption of the silver nano-grain colloid obtained is as shown in figure 11.
Embodiment 5.
The regular spherical silver nano-grain utilizing the technology of the present invention to prepare has multiple good characteristic, can be used to multinomial field.The regular spherical silver nano-grain colloid that the present embodiment introduction utilizes patent system of the present invention standby is to carry out an application of the Surface Enhanced Raman Scattering Spectrum detection of crystal violet molecule.
By the nano-silver colloid same 10 obtained under predose and 350mJ radiation parameter
-6crystal violet (the Crystalviolet of M, CV) solution mixing, drip on smooth high-purity aluminium flake of thickness 300 μm, purity 99.999%, carry out SERS experiment. the spectrum obtained as shown in figure 12: under 350mJ radiation parameter, the nano silver colloid of (a), predose (b) is SERS substrate, crystal violet molecule is probe, the SERS spectrum obtained, and crystal violet molecule (CV) Raman spectrum (c) not adding that substrate directly measures.
As can be seen from the figure, pure 10
-6the crystal violet solution of M does not have Raman signal.After mixing with silver colloidal solution, the Raman signal of CV is greatly strengthened, and obtains its SERS spectrum, as shown in Figure 12 (a, b).It is active that Ag colloidal solid namely after predose all has excellent SERS.But the SERS spectrum that contrast predose nano silver colloidal sol (a) obtains with the nano silver colloidal sol (b) obtained through 350mJ laser irradiation finds, at 418cm
-1, 688cm
-1, 1060cm
-1and 1448cm
-1position, there is obvious enhancing at the SERS peak after 350mJ laser irradiation than the Raman peaks that predose sample obtains.Meanwhile, at 443cm
-1, 1373cm
-1and 1537cm
-1position, after 350mJ irradiation compared with the sample of predose, there is by force obvious reduction at peak.
Vibration information corresponding to contrast crystal violet Raman peaks is known, and the crystal violet SERS spectrum that the regular spherical silver nano-grain after 350mJ laser irradiation detects as substrate compares the peak position (418cm of enhancing than the signal that the irregular pattern silver nano-grain of predose detects
-1, 688cm
-1, 1060cm
-1and 1448cm
-1) represent the vibration of central carbon atom and phenyl ring in crystal violet molecule, and the peak position (443cm weakened
-1, 1373cm
-1and 1537cm
-1) what then represent is the vibration information relevant to nitrogen-atoms.So the regular spherical silver nano-grain prepared by patent of the present invention can realize the specific adsorption of crystal violet molecule in SERS detection, thus there is potential using value for the precision detection of tiny signal.
Claims (9)
1. a preparation method for regular spherical silver nano-grain, is characterized in that, comprises the following steps:
10. prepare the irregular silver nano-grain precursor colloids of pattern, comprise the following steps:
Glass container is carried out alcohol and ultra-pure water ultrasonic cleaning successively by 101., adds the liquor argenti nitratis ophthalmicus that concentration is 0.51 ~ 0.53mmol/L, is positioned on electric furnace, is heated to boiling; Utilize separatory funnel, be that the sodium citrate solution of 3.4 ~ 3.7mmol/L dropwise joins in solution by concentration, utilize agitator to stir simultaneously; The volume ratio controlling liquor argenti nitratis ophthalmicus and sodium citrate solution is (45 ~ 50): 1;
After 102. reaction time 20 ~ 30min, close electric furnace, make the precursor colloids of preparation naturally cool to room temperature;
20. utilize presoma elargol to prepare regular spherical silver nano-grain, comprise the following steps:
The presoma elargol prepared is placed in open glass container by 201., and places it on horizontal rotating table, and setting speed is no more than 10r/min, and the colloidal solution degree of depth is no more than 3cm;
202. are blown into gas by the opposite direction that wireway rotates to open glass container to liquid surface, and make liquid unordered flowing in a reservoir, air velocity controls at 10cm
3/ s is advisable;
After 203. ventilation 1min, use the KrF PRK that wavelength is 248nm to carry out irradiation to forerunner's nanoparticles, control laser irradiation parameter in the process, it is 5 ~ 10Hz that pulse recurrence frequency controls, number of pulses 6000 ~ 8000;
After 204. irradiation terminate, stop ventilation, prepare the spherical silver nano-particle colloid of rule.
2. according to the method for claim 1, it is characterized in that, time prepared by forerunner's silver colloid, the reaction time is 25min.
3. according to the method for claim 1, it is characterized in that, time prepared by precursor colloids, the liquor argenti nitratis ophthalmicus concentration selected is 0.53mmol/L.
4. according to the method for claim 1, it is characterized in that, time prepared by precursor colloids, the sodium citrate solution concentration selected is 3.5mmol/L.
5. according to the method for claim 1, it is characterized in that, time prepared by presoma colloid, high density polyethylene (HDPE) material selected by agitator.
6. according to the method for claim 1, it is characterized in that, time prepared by precursor colloids, the liquor argenti nitratis ophthalmicus selected and the volume ratio of sodium citrate solution are 50:1.
7. according to the method for claim 1, it is characterized in that, in step 20, the gas that liquid surface passes in culture dish is N
2or air.
8. according to the method for claim 1, it is characterized in that, in step 20, the single pulse energy metric density of laser instrument should be 85 ~ 150mJ/cm
2.
9. according to the preparation-obtained regular spherical silver nano-grain colloid of method described in claim 1-8 and powder thereof.
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| CN111790918A (en) * | 2020-09-07 | 2020-10-20 | 西安宏星电子浆料科技股份有限公司 | Preparation method of silver powder with low thermal shrinkage |
| CN111790918B (en) * | 2020-09-07 | 2020-12-22 | 西安宏星电子浆料科技股份有限公司 | Preparation method of silver powder with low thermal shrinkage |
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