CN108115150A - A kind of preparation method of the nano silver of size adjustable - Google Patents
A kind of preparation method of the nano silver of size adjustable Download PDFInfo
- Publication number
- CN108115150A CN108115150A CN201711381953.7A CN201711381953A CN108115150A CN 108115150 A CN108115150 A CN 108115150A CN 201711381953 A CN201711381953 A CN 201711381953A CN 108115150 A CN108115150 A CN 108115150A
- Authority
- CN
- China
- Prior art keywords
- silver
- solution
- nano
- seed
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention discloses a kind of preparation method of the nano silver of size adjustable, this method comprises the following steps：Step 10) adds deionized water into container, and is heated to fluidized state；To sodium citrate solution is added in the deionized water of fluidized state, stabiliser solution is formed；Step 20) adds in silver-colored " seed " solution into stabiliser solution prepared by step 10), and AgNO is added in whipping process3Solution and quinol solution, and be kept stirring and fluidized state；Step 30) room temperature cooling step 20) prepare solution, be made spherical nano-silver.The preparation method can easily obtain the good spherical nano-silver of monodispersity, and the size of spherical nano-silver is adjustable extensively.
Description
Technical field
The present invention relates to a kind of preparation method of nano silver, it particularly relates to a kind of system of the nano silver of size adjustable
Preparation Method.
Background technology
Nano silver has the excellent physicochemical property for being different from its macroscopical block, in catalysis, biological and chemical sensor, light
The multiple fields such as picture, nonlinear optics, Surface enhanced Raman scattering, electronics are studied to be with a wide range of applications.At present, receive
Meter Yin, which has become, uses most materials in nanometer technology class consumer products.Substantial amounts of research shows the performance of nano silver
It is strongly depend on its shape and size.Therefore, the controllable preparation of nano silver is realized to the regulation and control of its performance and subsequent application
Prerequisite.From practical application, spherical nano silver is stablized, is easily prepared the most.It and can for the size of spherical nano-silver
Modulate it is standby, at present mostly using being carried out under organic solvent system, such as ethyl alcohol, ethylene glycol, oily amine toluene, 4- t-butyltoluenes
Deng.However the silver nano-grain prepared under organic solvent system is usually not easy to carry out water mutually to convert, and be difficult to follow-up
Water-wetted surface functional modification, seriously limit the application of nano silver.The use of organic solvent also be easy to cause environment simultaneously
Pollution.In contrast, synthesis in water spherical nano-silver has the potential advantages of bigger.Wherein reduction of sodium citrate method is that water is harmonious
Into the most frequently used of nanometer gold, silver and most easy method, i.e., under fluidized state, by metal precursor (gold chloride or silver nitrate)
Solution obtains nanogold or silver with sodium citrate solution reaction.Wherein, sodium citrate plays reducing agent, stabilizer and pH and adjusts
The multiple action of agent.Particularly, sodium citrate not only has splendid biocompatibility, simultaneously because citrate be it is a kind of compared with
Weak ligand is easier to other ligands or biomolecule be conducive to nanometer into line replacement to realize multi-functional surface modification
Application of the silver in biosystem.However, due to the silver-colored presoma such as silver nitrate have under water phase very high reactivity and
The non-single mode of action of citrate in the reaction so that the nucleation of nano silver and growth cannot be carried out controllably, easily be formed
The mixture of sizes and pattern.One of method for handling the above problem is separately to carry out the nucleation of nano silver and growth,
Use " seed " growth method：Strong reductant such as sodium borohydride (NaBH is used first4) synthesize the nano silver conduct of small size
" seed ", then using this " seed " as organic centre's continued growth, it is so that nucleation process and growth course is effectively separated, it is expected to
Realize prepared by the size adjustable of spherical nano-silver.Although the above method is in the spherical nano-silver side of growth small size (within 20nm)
Face is effective, when growing larger sized nano silver, secondary nucleation phenomenon significantly occurs for meeting, i.e., no longer with original " seed "
As organic centre, but substantial amounts of nano silver is spontaneously generated, this causes the spherical nano-silver size unevenness finally obtained together
And substantial amounts of number of other, non-spherical shapes is associated with, such as rodlike and flake nano silver.Therefore, to reduce the generation of secondary nucleation, in life
During long larger sized spherical nano-silver, the links such as step-by-step movement growth and multi-parameter modulation are usually inevitably needed.
Hydroquinone is that a kind of two contraposition hydrogen atoms of benzene are optionally substituted by a hydroxyl group the organic compound to be formed, soluble easily in water,
It is mainly used as the developer of photograph：In the case of there is silver-colored " seed " in the solution, hydroquinone is only on the surface of silver-colored " seed "
Silver-colored precursor in reducing solution forms silver-colored simple substance film.Due to hydroquinone have moderate oxidation-reduction potential (E °=-
0.699V vs NHE,Ag+/Ag0, E °=+ 0.799V), the above process can quickly carry out (1) at normal temperatures.Similarly, it is above-mentioned
Strategy is also applied under room temperature to the preparation (AuCl of golden film4 -/Au0, E °=+ 1.002V) and (2).
Particularly, hydroquinone and its oxidation product benzoquinones only have metal surface very weak suction-operated, are reacting
If there is the stabilizer (such as citrate) of stronger suction-operated in system, you can by absorption competition effect substitution to benzene two
The suction-operated of phenol and benzoquinones forms the nano material that citrate is stablized.Based on two above-mentioned characteristics of hydroquinone, in recent years
Come, people have been attempted using hydroquinone as selective reduction agent, and sodium citrate is for stabilizer by " seed " method in normal temperature condition
The lower nanometer gold, silver for preparing sodium citrate stabilization.However, although above-mentioned hydroquinone-" seed " method strategy realizes citric acid
Prepared by the large range of size adjustable of the ball shaped nano gold of stable sodium, but when preparing spherical nano-silver, the product of acquisition is then
There are size adjustable scope is very limited and with serious problems such as a large amount of flake nano silvers.
The content of the invention
Technical problem：The technical problems to be solved by the invention are：A kind of preparation side of the nano silver of size adjustable is provided
Method can easily prepare the good spherical nano-silver of monodispersity, and the size of spherical nano-silver is adjustable extensively.
In order to solve the above technical problems, the technical solution that uses of the embodiment of the present invention for：
A kind of preparation method of the nano silver of size adjustable, this method comprise the following steps：
Step 10) adds deionized water into container, and is heated to fluidized state；To the deionized water in fluidized state
Middle addition sodium citrate solution forms stabiliser solution；
Step 20) adds in silver-colored " seed " solution into stabiliser solution prepared by step 10), is added in whipping process
AgNO3Solution and quinol solution, and be kept stirring and fluidized state；
Step 30) room temperature cooling step 20) prepare solution, be made spherical nano-silver.
As preference, the container has effects that reflux.
As preference, in the step 20), in final reaction solution, AgNO3Molar ratio with hydroquinone is
1:2。
As preference, in the step 20), in final reaction solution, the molar ratio of sodium citrate and silver nitrate
For 0.2~0.3:1.
As preference, described silver " seed " solution is prepared as follows：By deionized water and sodium citrate solution
Mixing after stirring, forms stabiliser solution；Stabiliser solution is heated to the temperature of water-bath, then adds in AgNO3Solution, then add
Enter NaBH4Solution；After room temperature cooling, with deionized water constant volume, silver " seed " solution is made.
As preference, in the step 20), AgNO is first added in3Solution, after be added immediately quinol solution.
Advantageous effect：Compared with prior art, the invention has the advantages that：
The preparation method of the embodiment of the present invention can easily prepare the good spherical nano-silver of monodispersity, and spherical
The size of nano silver is adjustable extensively.For the present invention using silver nitrate as the presoma of silver, sodium citrate is stabilizer, and hydroquinone is choosing
Selecting property reducing agent, " seed " growth method under being flowed back by heat effectively separate two processes of nucleation and growth of nano silver,
And the generation of secondary nucleation is avoided, successfully prepares the good nano silver of monodispersity.In the preparation method of the present invention, lead to
Cross the dosage of the silver " seed " in only changing the step 20), the proportioning of silver nitrate and sodium citrate in it need not change growth-promoting media
In the case of, by a step " seed " growth course, a series of good spherical shape of monodispersity for having prepared size adjustables is received
Meter Yin, need not the usually necessary multiple link grown and multi-parameter is adjusted.
Description of the drawings
Fig. 1 (a) is that the transmission electron microscope of nano silver prepared by embodiment 1 characterizes photo；
Fig. 1 (b) is that the transmission electron microscope of nano silver prepared by embodiment 2 characterizes photo；
Fig. 1 (c) is that the transmission electron microscope of nano silver prepared by embodiment 3 characterizes photo；
Fig. 1 (d) is that the transmission electron microscope of nano silver prepared by embodiment 4 characterizes photo；
Fig. 2 (a) is that the transmission electron microscope of nano silver prepared by comparative example 1 characterizes photo；
Fig. 2 (b) is that the transmission electron microscope of nano silver prepared by comparative example 2 characterizes photo；
Fig. 2 (c) is that the transmission electron microscope of nano silver prepared by comparative example 3 characterizes photo；
Fig. 2 (d) is that the transmission electron microscope of nano silver prepared by comparative example 4 characterizes photo；
Fig. 2 (d) is that the transmission electron microscope of nano silver prepared by comparative example 4 characterizes photo；
Fig. 3 is the UV-Vis spectra figure of nano silver prepared by 1-embodiment of embodiment 4；
Fig. 4 is the UV-Vis spectra figure of nano silver prepared by 1-comparative example of comparative example 4；
Fig. 5 (a) is that the transmission electron microscope of nano silver prepared by embodiment 5 characterizes photo；
Fig. 5 (b) is that the transmission electron microscope of nano silver prepared by embodiment 6 characterizes photo；
Fig. 5 (c) is that the transmission electron microscope of nano silver prepared by embodiment 7 characterizes photo；
Fig. 5 (d) is that the transmission electron microscope of nano silver prepared by embodiment 8 characterizes photo；
Fig. 6 is that the transmission electron microscope of nano silver prepared by comparative example 5 characterizes photo；
Fig. 7 is that the transmission electron microscope of nano silver prepared by comparative example 6 characterizes photo.
Specific embodiment
Technical scheme is described in detail below.
A kind of preparation method of the nano silver of size adjustable of the embodiment of the present invention, comprises the following steps：
Step 10) adds deionized water into container, and is heated to fluidized state；To the deionized water in fluidized state
Middle addition sodium citrate solution forms stabiliser solution；
Step 20) adds in silver-colored " seed " solution into stabiliser solution prepared by step 10), is added in whipping process
AgNO3Solution and quinol solution, and be kept stirring and fluidized state；
Step 30) room temperature cooling step 20) prepare solution, be made spherical nano-silver.
In above-mentioned preparation method, in the presence of silver-colored " seed ", hydroquinone is to AgNO3Reproducibility be far above citric acid
Sodium.After adding in quinol solution in reaction solution, since hydroquinone is only in silver-colored " seed " surface reduction AgNO3For silver atoms,
The silver atoms of generation for core continuous deposition, cause silver-colored " seed " gradually to grow up with silver-colored " seed ".Above-mentioned response characteristic is by nanometer
Two processes of nucleation and growth of silver effectively separate, and avoid the generation of secondary nucleation.Hydroquinone is in fluidized state
Under still keep the ability of selective reduction (i.e. in its surface reduction AgNO only under the conditions of silver-colored " seed " is existing3).According to model
Special Hough rule, temperature often raise 10 degree, react and usually accelerate 2~4 times.Simple calculate understands, (is set under fluidized state
100 DEG C) reaction rate be about 128 times under room temperature (being set to 30 DEG C).Under high reaction rate, silver atoms are in silver-colored " seed " table
Face will be not added with distinguishing crystal face, non-selectivity central symmetry deposition, form thermodynamically stable spherical nano-silver, eliminate aspheric
Shape structure, such as the formation of Nano silver piece or Silver nanorod.On the other hand, hydroquinone and its oxidation product benzoquinones are to metal surface
Adsorption capacity be far weaker than sodium citrate, therefore sodium citrate only serves the effect of stabilizer.Therefore, citric acid is ultimately formed
The spherical nano-silver of stable sodium.
For the embodiment using silver nitrate as the presoma of silver, sodium citrate is stabilizer, and hydroquinone is selective reduction agent,
Two processes of nucleation and growth of nano silver are effectively separated, and avoid two by the seed mediated growth method under being flowed back by heat
The good nano silver of monodispersity is prepared in the generation of secondary nucleation.The good spherical nano-silver of monodispersity due to individual shapes,
Size uniformity has fully ensured that the reliability of its various physicochemical property, increases such as, but not limited to optics, electricity, catalysis, surface
The properties such as strong Raman scattering, antibacterial/antibacterial, are particularly conducive to practical application.Nano silver prepared by the embodiment is steady for thermodynamics
Fixed spherical nano-silver.
The preparation method of the embodiment can prepare size adjustable spherical nano-silver extensively.Do not changing other reaction ginsengs
In the case of number, the amount only by changing silver-colored " seed ", you can adjusted extensively to the size of spherical nano-silver.
In above-described embodiment, the container has effects that reflux.For example, container uses the container with condenser pipe.This reality
In the preparation process for applying example, solution is in fluidized state.The steam of solution explosive evaporation runs into condenser pipe, becomes liquid, and returns
It flow in container, so that the volume of solution remains unchanged afterwards before the reaction.
In above-described embodiment, in step 20), in final reaction solution, AgNO3Molar ratio with hydroquinone is 1:
2.It can so ensure to react abundant progress.In final reaction solution, the molar ratio of sodium citrate and silver nitrate for 0.2~
0.3:1.This had both ensured stabilization of the sodium citrate to nano silver, and prevented sodium citrate and silver nitrate during charging
It reacts.
There are many preparation methods of silver-colored " seed " solution.The preferably following preparation method of the present embodiment：By deionized water and lemon
Lemon acid sodium solution mixes, and after stirring, forms stabiliser solution；Stabiliser solution is heated to the temperature of water-bath, then adds in AgNO3
Solution adds NaBH4Solution；After room temperature cooling, with deionized water constant volume, silver seed solution is made.
Such as：Prepare silver-colored seed solution：By the citric acid that the deionized water of 60~80mL and 20mL mass volume ratios are 1%
Sodium solution mixes, and after stirring evenly, forms stabiliser solution；Under 70~80 DEG C of water-bath, water is heated to stabiliser solution
Then the temperature of bath adds in the AgNO that 1.7mL mass volume ratios are 1% into the stabiliser solution3Solution；In mechanical agitation stick
Stirring under, then the NaBH that 1.5~2.5mL mass volume ratios are 0.1% is added in into the stabiliser solution4Solution, and stir
60min~120min；It is molten so as to which silver-colored " seed " be made with deionized water constant volume to 100mL after finally solution room temperature is cooled down
Liquid.
This method can prepare stable, narrow size distribution silver " seed ".In this method, using depositing in sodium citrate
Under, fast reaction combines the reactive mode of heating curing, and the presence of a large amount of sodium citrates extremely effective can prevent from generating
Silver " seed " it is oversized.Utilize NaBH4Strong reducing action, make AgNO3It is nucleated by quick reduction and grows up to nano particle.
Generated silver " seed " is driven further to cure in a heated condition, the ablation in laser outfield is equivalent to, so that most
Whole product has good monodispersity.This method can obtain that stability is good, silver " seed " of narrow size distribution, silver
" seed " average-size can ensure in 4nm.The preparation method is the prior art, reference can be made to patent No. ZL201210183257.6
Chinese patent.Silver " seed " preparation method introduced in the patent can be applied in the present invention.
In above-described embodiment step 20), AgNO is first added in3Solution adds in quinol solution afterwards.Because first add in AgNO3
Solution makes its full and uniform dispersion in reaction solution around added silver " seed ", and the hydroquinone added in after being convenient for is molten
Liquid is to it uniformly in silver-colored " seed " surface reduction.
The preparation method of above-described embodiment can prepare stable, the silver " seed " of the high quality of narrow size distribution.This hair
It in bright preparation method, takes in the presence of a large amount of sodium citrates, fast reaction combines the reactive mode of heating curing, mistake
Amount sodium citrate extremely effective can prevent that the silver " seed " of generation is oversized.Preferably, the method for the present embodiment makes
Sodium citrate mass concentration is required by traditional Citrate Buffer (comparative example 5 of process following article) prepares nano silver
10~15 times of sodium citrate mass concentration.Utilize NaBH4Strong reducing action, make AgNO3It is nucleated and is grown up to by quick reduction and receive
Meter Yin.Generated silver " seed " is driven further to cure under suitable heating condition, the ablation for being equivalent to laser outfield is made
With so that final product has good monodispersity.The preparation method of the present invention can obtain that stability is good, size point
The narrow silver of cloth " seed ", silver-colored " seed " average-size can be controlled in 4nm or so.
The preparation method of above-described embodiment is environmentally friendly, efficient.The preparation of the spherical nano-silver of size adjustable provided by the invention
Method, in the growth course of nano silver, it is only necessary to which silver nitrate is as oxidant, sodium citrate as stabilizer and to benzene two
Phenol alternatively property reducing agent, it is whole to swash without introducing without special reaction unit (electric jacket or electric furnace during heating)
The outfields such as light ablation aid in, without the additional auxiliary agent (high molecular surfactants such as such as polyvinylpyrrolidone, polyethylene glycol
Or other auxiliary agents such as small molecule or ion such as NaCl, NaBr control the shape of nano silver) and without by acid, aqueous slkali
The pH value of regulation system, preparation method environmental protection, efficiently, can the amount of expansion carry out.
The preparation method of above-described embodiment can be prepared in the case where only needing to change " seed " addition with monodispersity
Good spherical shape silver nano-grain, and the size of spherical nano-silver is adjustable extensively, need not usually necessary multiple growth and
The step of multi-parameter is adjusted.
Good result possessed by the embodiment of the present invention is verified below by specific experiment.
Embodiment 1
Prepare spherical nano-silver：60~80mL deionized waters are added into container, and are heated to fluidized state；To in boiling
The sodium citrate solution for adding in that 0.25mL molar concentrations are 0.1M in the deionized water of state is risen, forms stabiliser solution；Xiang Wen
Determine to add in silver-colored " seed " solution of 1.0mL in agent solution, the AgNO that 1.0mL molar concentrations are 0.1M is added in whipping process3It is molten
Liquid and 1.0mL molar concentrations are the quinol solution of 0.05M, and are kept stirring and fluidized state 60min；Room temperature cooling is molten
Spherical nano-silver is made in liquid.
Embodiment 2
Prepare spherical nano-silver：60~80mL deionized waters are added into container, and are heated to fluidized state；To in boiling
The sodium citrate solution for adding in that 0.25mL molar concentrations are 0.1M in the deionized water of state is risen, forms stabiliser solution；Xiang Wen
Determine to add in silver-colored " seed " solution of 2.5mL in agent solution, the AgNO that 1.0mL molar concentrations are 0.1M is added in whipping process3It is molten
Liquid and 1.0mL molar concentrations are the quinol solution of 0.05M, and are kept stirring and fluidized state 60min；Room temperature cooling is molten
Spherical nano-silver is made in liquid.
Embodiment 3
Prepare spherical nano-silver：60~80mL deionized waters are added into container, and are heated to fluidized state；To in boiling
The sodium citrate solution for adding in that 0.25mL molar concentrations are 0.1M in the deionized water of state is risen, forms stabiliser solution；Xiang Wen
Determine to add in silver-colored " seed " solution of 5mL in agent solution, the AgNO that 1.0mL molar concentrations are 0.1M is added in whipping process3Solution
It is the quinol solution of 0.05M with 1.0mL molar concentrations, and is kept stirring and fluidized state 60min；Room temperature cools down solution,
Spherical nano-silver is made.
Embodiment 4
Prepare spherical nano-silver：60~80mL deionized waters are added into container, and are heated to fluidized state；To in boiling
The sodium citrate solution for adding in that 0.25mL molar concentrations are 0.1M in the deionized water of state is risen, forms stabiliser solution；Xiang Wen
Determine to add in silver-colored " seed " solution of 10mL in agent solution, the AgNO that 1.0mL molar concentrations are 0.1M is added in whipping process3Solution
It is the quinol solution of 0.05M with 1.0mL molar concentrations, and is kept stirring and fluidized state 60min；Room temperature cools down solution,
Spherical nano-silver is made.
Embodiment 5
Prepare spherical nano-silver：60~80mL deionized waters are added into container, and are heated to fluidized state；To in boiling
The sodium citrate solution for adding in that 0.25mL molar concentrations are 0.1M in the deionized water of state is risen, forms stabiliser solution；Xiang Wen
Determine to add in silver-colored " seed " solution of 30mL in agent solution, the AgNO that 1.0mL molar concentrations are 0.1M is added in whipping process3Solution
It is the quinol solution of 0.05M with 1.0mL molar concentrations, and is kept stirring and fluidized state 60min；Room temperature cools down solution,
Spherical nano-silver is made.
Embodiment 6
Prepare spherical nano-silver：60~80mL deionized waters are added into container, and are heated to fluidized state；To in boiling
The sodium citrate solution for adding in that 0.25mL molar concentrations are 0.1M in the deionized water of state is risen, forms stabiliser solution；Xiang Wen
Determine to add in 0.5mL silver seed solutions in agent solution, the AgNO that 1.0mL molar concentrations are 0.1M is added in whipping process3Solution
It is the quinol solution of 0.05M with 1.0mL molar concentrations, and is kept stirring and fluidized state 60min；Room temperature cools down solution,
Spherical nano-silver is made.
Embodiment 7
Prepare spherical nano-silver：60~80mL deionized waters are added into container, and are heated to fluidized state；To in boiling
The sodium citrate solution for adding in that 0.25mL molar concentrations are 0.1M in the deionized water of state is risen, forms stabiliser solution；Xiang Wen
Determine to add in silver-colored " seed " solution of 0.1mL in agent solution, the AgNO that 1.0mL molar concentrations are 0.1M is added in whipping process3It is molten
Liquid and 1.0mL molar concentrations are the quinol solution of 0.05M, and are kept stirring and fluidized state 60min；Room temperature cooling is molten
Spherical nano-silver is made in liquid.
Embodiment 8
Prepare spherical nano-silver：60~80mL deionized waters are added into container, and are heated to fluidized state；To in boiling
The sodium citrate solution for adding in that 0.25mL molar concentrations are 0.1M in the deionized water of state is risen, forms stabiliser solution；Xiang Wen
Determine to add in silver-colored " seed " solution of 0.015mL in agent solution, the AgNO that 1.0mL molar concentrations are 0.1M is added in whipping process3
Solution and 1.0mL molar concentrations are the quinol solution of 0.05M, and are kept stirring and fluidized state 60min；Room temperature cooling is molten
Spherical nano-silver is made in liquid.
Comparative example 1
Using hydroquinone as reducing agent under traditional room temperature, sodium citrate is stabilizer, and silver nitrate is prepared for oxidant
Nano silver：Process is same as the previously described embodiments, but (30 DEG C) progress at normal temperatures.Wherein, it is 1mL to add in silver-colored " seed ".
Comparative example 2
It is identical with comparative example 1, except that it is 2.5mL to add in silver-colored " seed " solution.
Comparative example 3
It is identical with comparative example 1, except that it is 5mL to add in silver-colored " seed " solution.
Comparative example 4
It is identical with comparative example 1, except that it is 10mL to add in silver-colored " seed " solution.
Comparative example 5
Traditional Citrate Buffer prepares nano silver：18 milligrams of AgNO3It is dissolved in 100mL deionized waters and is heated to boil
It rises, then adds in the sodium citrate solution that 2mL mass volume ratios are 1%, react 60min, room temperature under boiling and lasting stirring
Solution is cooled down, obtains the nano silver of sodium citrate stabilization.Bibliography：P.C.Lee,D.Meisel,Adsorption and
surface-enhanced Raman of dyes on silver and gold sols,J.Phys.Chem.86(1982)
3391-3395.
Comparative example 6
Conventional silver " seed " growth method prepares the nano silver of sodium citrate stabilization：Into container add 60~80mL go from
Then sub- water adds in the sodium citrate solution that 2mL mass volume ratios are 1% into deionized water, form reducing agent solution, heating
The reducing agent solution is to fluidized state；Silver " seed " solution 1mL is added in into above-mentioned reducing agent solution, in whipping process, is added
Enter the AgNO that 1.7mL mass volume ratios are 1%3Solution is kept stirring and fluidized state 60min.Room temperature cools down solution, obtains lemon
The nano silver of sour stable sodium.
Bibliography：Y.Wan,Z.Guo,X.Jiang,K.Fang,X.Lu,Y.Zhang,N.Gu,Quasi-spherical
silvernanoparticles:Aqueous synthesis and size control by theseed-mediated
Lee-Meisel method,J.Colloid Interface Sci.394(2013)263-268.
Transmission electron microscope characterization shooting is carried out to nano silver prepared by embodiment 1 to embodiment 4.Transmission electron microscope characterization photo is such as
Shown in Fig. 1 (a)-(d).Wherein, the transmission electron microscope characterization photo of nano silver prepared by embodiment 1 is Fig. 1 (a), prepared by embodiment 2
Nano silver transmission electron microscope characterization photo be Fig. 1 (b), embodiment 3 prepare nano silver transmission electron microscope characterization photo be Fig. 1
(c), the transmission electron microscope characterization photo of nano silver prepared by embodiment 4 is Fig. 1 (d).
Transmission electron microscope characterization shooting is carried out to nano silver prepared by comparative example 1 to comparative example 4.Transmission electron microscope characterization photo is such as
Shown in Fig. 2 (a)-(d).Wherein, the transmission electron microscope characterization photo of nano silver prepared by comparative example 1 is Fig. 2 (a), prepared by comparative example 1
Nano silver transmission electron microscope characterization photo be Fig. 2 (b), comparative example 3 prepare nano silver transmission electron microscope characterization photo be Fig. 2
(c), the transmission electron microscope characterization photo of nano silver prepared by comparative example 4 is Fig. 2 (d).
Spherical form is presented in the nano silver that embodiment 1 is prepared to embodiment 4 it can be seen from Fig. 1 (a)-(d), and
Size Distribution is homogeneous.Then comprising substantial amounts of in the nano silver prepared by comparative example it can be seen from Fig. 2 (a)-(d) 1 to comparative example 4
Aspherical Nano silver piece structure.
In order to further compare, Nano silver solution that we respectively prepare embodiment 1 to embodiment 4 and comparative example 1 to
Nano silver solution prepared by comparative example 4 has carried out Spectroscopic Characterization.The nanometer that embodiment 1 is prepared to embodiment 4 is shown in Fig. 3
The UV-Vis spectra figure of silver.The ultraviolet-visible light light of nano silver prepared by comparative example 1 to comparative example 4 is shown in Fig. 4
Spectrogram.
As seen from Figure 3, point is presented in the UV-Vis spectra figure for the nano silver that embodiment 1 is prepared to embodiment 4
Sharp, symmetrical peak type.This illustrates that the nano silver prepared has good monodispersity.The transmission electron microscope results of this and Fig. 1 characterize
Unanimously.As seen from Figure 4, the UV-Vis spectra figure peak type for the nano silver that comparative example 1 is prepared to comparative example 4 is significantly opened up
Width, and with the appearance of acromion.This illustrates that the nano silver monodispersity prepared is poor, and contains number of other, non-spherical shapes.This is demonstrated
The transmission electron microscope characterization result of Fig. 2.
Transmission electron microscope characterization shooting is carried out to nano silver prepared by embodiment 5 to embodiment 8.Transmission electron microscope characterization photo is such as
Shown in Fig. 5 (a)-(d).Wherein, the transmission electron microscope characterization photo of nano silver prepared by embodiment 5 is Fig. 5 (a), prepared by embodiment 6
Nano silver transmission electron microscope characterization photo be Fig. 5 (b), embodiment 7 prepare nano silver transmission electron microscope characterization photo be Fig. 5
(c), the transmission electron microscope characterization photo of nano silver prepared by embodiment 8 is Fig. 5 (d).It can be seen that from Fig. 5 (a)-(d)：Only
In the case of changing " seed " addition, it can prepare with the good spherical nano-silver of monodispersity, and spherical nano-silver
Size is adjustable extensively in the range of 15nm-150nm.
Transmission electron microscope characterization shooting is carried out to nano silver prepared by comparative example 5 and comparative example 6.Nanometer prepared by comparative example 5
The transmission electron microscope characterization photo of silver is shown in Fig. 6.The transmission electron microscope characterization photo of nano silver prepared by comparative example 6 is shown in Fig. 7.
As can be seen from Figure 6：Traditional Citrate Buffer prepares nano silver and is difficult to control in shape and size.As can be seen from Figure 7：
The nano silver that conventional silver " seed " growth method prepares sodium citrate stabilization shows since secondary nucleation in preparation process, easily occurs
As so as to cause a large amount of generations of number of other, non-spherical shapes such as Silver nanorod.
The basic principles, main features and advantages of the invention have been shown and described above.Those skilled in the art should
Understand, the present invention from above-mentioned specific embodiment limitation, the description in above-mentioned specific embodiment and specification be intended merely into
One step illustrates the principle of the present invention, without departing from the spirit and scope of the present invention, the present invention also have various change and
It improves, these changes and improvements all fall within the protetion scope of the claimed invention.The scope of protection of present invention will by right
Ask book and its equivalent thereof.
Claims (6)
1. a kind of preparation method of the nano silver of size adjustable, which is characterized in that this method comprises the following steps：
Step 10) adds deionized water into container, and is heated to fluidized state；Add in the deionized water of fluidized state
Enter sodium citrate solution, form stabiliser solution；
Step 20) adds in silver-colored " seed " solution into stabiliser solution prepared by step 10), and AgNO is added in whipping process3It is molten
Liquid and quinol solution, and be kept stirring and fluidized state；
Step 30) room temperature cooling step 20) prepare solution, be made spherical nano-silver.
2. the preparation method of the nano silver of size adjustable described in accordance with the claim 1, which is characterized in that the container has back
Flow effect.
3. the preparation method of the nano silver of size adjustable described in accordance with the claim 1, which is characterized in that in the step 20),
In final reaction solution, AgNO3Molar ratio with hydroquinone is 1:2.
4. the preparation method of the nano silver of size adjustable described in accordance with the claim 1, which is characterized in that in the step 20),
In final reaction solution, the molar ratio of sodium citrate and silver nitrate is 0.2~0.3:1.
5. the preparation method of the nano silver of size adjustable described in accordance with the claim 1, which is characterized in that the silver " seed " is molten
Liquid is prepared as follows：
Deionized water with sodium citrate solution is mixed, after stirring, forms stabiliser solution；Stabiliser solution is heated to water-bath temperature
Degree, then adds in AgNO3Solution adds NaBH4Solution；After room temperature cooling, with deionized water constant volume, it is molten that silver " seed " is made
Liquid.
6. the preparation method of the nano silver of size adjustable described in accordance with the claim 1, which is characterized in that in the step 20),
First add in AgNO3Solution, after be added immediately quinol solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711381953.7A CN108115150B (en) | 2017-12-20 | 2017-12-20 | Preparation method of nano silver with adjustable size |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711381953.7A CN108115150B (en) | 2017-12-20 | 2017-12-20 | Preparation method of nano silver with adjustable size |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108115150A true CN108115150A (en) | 2018-06-05 |
| CN108115150B CN108115150B (en) | 2023-08-08 |
Family
ID=62230427
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711381953.7A Active CN108115150B (en) | 2017-12-20 | 2017-12-20 | Preparation method of nano silver with adjustable size |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108115150B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109500404A (en) * | 2018-12-24 | 2019-03-22 | 山东大学 | The synthetic method of water-soluble mono dispersion large scale spherical shape silver nano-grain |
| CN110355380A (en) * | 2019-08-13 | 2019-10-22 | 山东建邦胶体材料有限公司 | A kind of preparation method of hexagonal flake micron crystalline substance silver powder |
| CN113425851A (en) * | 2021-07-09 | 2021-09-24 | 南京市儿童医院 | Preparation method and application of BIX-01294 modified gold nano-star |
| CN114131037A (en) * | 2021-12-07 | 2022-03-04 | 南京医科大学第二附属医院 | Preparation method of gold-silver alloy nanoshell with high SERS activity |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1461176A (en) * | 1974-04-11 | 1977-01-13 | Plessey Inc | Method of producing powdered materials |
| CN1227148A (en) * | 1999-01-19 | 1999-09-01 | 沈阳黎明发动机制造公司 | High purity high dispersiveness spherical super fine silver powder and its producing method |
| CN102672200A (en) * | 2012-06-06 | 2012-09-19 | 南京医科大学第二附属医院 | Water phase preparation method of spherical silver nanoparticle with adjustable size |
| CN103722181A (en) * | 2014-01-21 | 2014-04-16 | 江苏欧耐尔新型材料有限公司 | Method for preparing nano silver powder by using dispersing agent through liquid-phase reduction method |
| CN105108171A (en) * | 2015-09-24 | 2015-12-02 | 厦门大学 | Preparing method for nanometer particles with strong Raman signals |
-
2017
- 2017-12-20 CN CN201711381953.7A patent/CN108115150B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1461176A (en) * | 1974-04-11 | 1977-01-13 | Plessey Inc | Method of producing powdered materials |
| CN1227148A (en) * | 1999-01-19 | 1999-09-01 | 沈阳黎明发动机制造公司 | High purity high dispersiveness spherical super fine silver powder and its producing method |
| CN102672200A (en) * | 2012-06-06 | 2012-09-19 | 南京医科大学第二附属医院 | Water phase preparation method of spherical silver nanoparticle with adjustable size |
| CN103722181A (en) * | 2014-01-21 | 2014-04-16 | 江苏欧耐尔新型材料有限公司 | Method for preparing nano silver powder by using dispersing agent through liquid-phase reduction method |
| CN105108171A (en) * | 2015-09-24 | 2015-12-02 | 厦门大学 | Preparing method for nanometer particles with strong Raman signals |
Non-Patent Citations (2)
| Title |
|---|
| 孙永兴: "粒径可控球形密实银粉的制备研究", 《硕士论文》 * |
| 李明利等: "球形纳米银粉的制备与微结构研究", 《兵器材料科学与工程》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109500404A (en) * | 2018-12-24 | 2019-03-22 | 山东大学 | The synthetic method of water-soluble mono dispersion large scale spherical shape silver nano-grain |
| CN110355380A (en) * | 2019-08-13 | 2019-10-22 | 山东建邦胶体材料有限公司 | A kind of preparation method of hexagonal flake micron crystalline substance silver powder |
| CN113425851A (en) * | 2021-07-09 | 2021-09-24 | 南京市儿童医院 | Preparation method and application of BIX-01294 modified gold nano-star |
| CN113425851B (en) * | 2021-07-09 | 2021-12-17 | 南京市儿童医院 | Preparation method and application of BIX-01294 modified gold nano-star |
| CN114131037A (en) * | 2021-12-07 | 2022-03-04 | 南京医科大学第二附属医院 | Preparation method of gold-silver alloy nanoshell with high SERS activity |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108115150B (en) | 2023-08-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102672200B (en) | Water phase preparation method of spherical silver nanoparticle with adjustable size | |
| CN108115150A (en) | A kind of preparation method of the nano silver of size adjustable | |
| Tang et al. | Poly (N-vinyl-2-pyrrolidone)(PVP)-capped dendritic gold nanoparticles by a one-step hydrothermal route and their high SERS effect | |
| Oh et al. | Chemically tailorable colloidal particles from infinite coordination polymers | |
| Zheng et al. | Successive, seed‐mediated growth for the synthesis of single‐crystal gold nanospheres with uniform diameters controlled in the range of 5–150 nm | |
| Mdluli et al. | Selective adsorption of PVP on the surface of silver nanoparticles: a molecular dynamics study | |
| JP4748989B2 (en) | Method for the synthesis of metal nanoparticles | |
| Jimenez‐Ruiz et al. | Nonfunctionalized gold nanoparticles: synthetic routes and synthesis condition dependence | |
| Dong et al. | Facile and one-step synthesis of monodisperse silver nanoparticles using gum acacia in aqueous solution | |
| JP4774214B2 (en) | Method for synthesizing metal nanoparticles | |
| Kundu et al. | Shape-selective formation and characterization of catalytically active iridium nanoparticles | |
| CN105328206A (en) | Method for preparing copper nanowires through oil-phase chemical reduction | |
| TW200839042A (en) | Process for the synthesis of nanoscale, metal-containing nanoparticles and nanoparticle dispersions | |
| CN107377993B (en) | A kind of metal nanometer line, dispersion liquid and preparation method thereof | |
| CN101492164A (en) | Method of manufacturing monodisperse silicon dioxide microsphere | |
| CN106811832B (en) | A kind of pearl-decorated curtain shape BiFeO3The preparation method and products obtained therefrom of micro nanometer fiber | |
| CN105127446A (en) | Precious-metal nanometer bipyramid and preparing method thereof | |
| CN106112009A (en) | A kind of rhodio-platinum alloy nano flower and preparation method thereof | |
| He et al. | Continuous, size and shape-control synthesis of hollow silica nanoparticles enabled by a microreactor-assisted rapid mixing process | |
| CN100431752C (en) | Method for preparing single dispersion triangular nano silver slice | |
| CN111702186A (en) | Preparation method of gold nanoparticles with adjustable size | |
| CN107866577B (en) | Method for preparing monodisperse silver powder by instant micro-flow reactor | |
| CN104551008A (en) | Adjustable spectrum gold nanoshell preparation method | |
| Do Thi et al. | Seeded Growth Synthesis of Uniform Gold Nanoparticles with Controlled Diameters up to 220 nm | |
| CN104609431A (en) | Synthetic method and particle size control synthetic method for SiO2 nano particles smaller than 50 nm |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |