CN103143721A - Preparation method of Ag@SiO2 core-shell structure nano composite - Google Patents
Preparation method of Ag@SiO2 core-shell structure nano composite Download PDFInfo
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- CN103143721A CN103143721A CN2013100822478A CN201310082247A CN103143721A CN 103143721 A CN103143721 A CN 103143721A CN 2013100822478 A CN2013100822478 A CN 2013100822478A CN 201310082247 A CN201310082247 A CN 201310082247A CN 103143721 A CN103143721 A CN 103143721A
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Abstract
The invention relates to a preparation method of an Ag@SiO2 core-shell structure nano composite, which is characterized in that an inverse micro-emulsion method serves as a template; NaBH4 serves as a reducing agent; AgNO3 serves as an Ag precursor; tetraethoxysilane (TEOS) serves as an SiO2 precursor; ammonia water serves as a catalyst; continuous sampling is conducted; and generation of Ag nanocrystallines and covering of SiO2 shells are conducted in one reactor. The prepared Ag@SiO2 core-shell composite is regular in pattern, and has an appreciable material property; the pattern and a dimension of the Ag@SiO2 core-shell composite can be adjusted conveniently by changing a technological condition; and the synthesized Ag@SiO2 core-shell structure nano composite by the method is simple in technology, low in equipment requirement, high in production efficiency and low in cost.
Description
Technical field
The present invention relates to a kind of Ag@SiO
2The preparation method of nuclear-shell structured nano-composite material belongs to the nano material preparing technical field.
Background technology
In recent years, the preparation of nuclear-shell structured nano-composite material (especially metal/oxide core-shell nano composite) has caused that people study interest widely, it is the important constituent element of constructing the new function composite, in fields such as photonic bandgap material, microwave absorbing material, catalyst and biologies, important application is arranged.Nuclear-shell structured nano-composite material, its inside and outside enrichment heterogeneity respectively demonstrates special bilayer or sandwich construction.Compound and complementary by the function of core and shell, modulate the new function material of the performance that is different from core or shell itself, for the design of new material provides approach very easily.
Nano Silver refers to that particle diameter is the argent simple substance of 1～100nm, is a kind of emerging and widely used metal material.Nano Silver has very high specific area and surface-active, and conductance is higher at least 20 times than common silver, and therefore, Nano Silver receives people's concern because of the characteristics such as heat, light, electricity, magnetic, catalysis and sensitivity of its uniqueness, be widely used as catalyst material.Antistatic material, low temperature superconducting material and biology sensor material etc.In addition, Nano Silver also has antibacterial functions and good bio-compatibility, can be used for pharmaceuticals industry.Yet usually the research of the optical property of silver particles mainly is confined in glass or aqueous solution medium, in this case, the absworption peak that the surface plasma body resonant vibration of silver particles causes is in about 400nm, therefore changes its surrounding medium and is significant to developing new optical function material to change its absworption peak position.
SiO
2A kind of have good optics and mechanical performance, chemical stability, stable on heating insulator.Usually the SiO that adopts in functional material
2Mostly be unformed shape, this amorphous Si O
2Has good light sensitivity and the wide spectrum transparency.Therefore, amorphous SiO
2Have a wide range of applications in the Related products such as light, electrical component, low reflectance coating, insulating barrier, diffusion blocking film.It should be noted that and work as amorphous SiO
2When carrying out some special doping treatment, the optical property of himself will obtain significant the raising or change, thereby, amorphous Si O
2Also has good performance adjustability.Therefore, select suitable material and amorphous Si O
2Compound, often can prepare excellent optical performance, and have the high stability advanced composite material (ACM) of other physical property concurrently.
Ag@SiO
2The nucleocapsid structure material is with the continuous amorphous SiO that is distributed in of nanoscale Ag uniform particles disperse
2Among matrix, effectively controlled the reunion of Ag nano particle and grown up, simultaneously amorphous SiO
2Be wrapped in the Ag nano particle around, improved significantly the stability of Ag nano particle, and improved the surface characteristic of Ag nano particle, thereby made the practicality of Ag nano particle obtain greatly to promote.
The preparation method of metal/silica core-shell nano is mainly liquid phase deposition, and in absolute ethyl alcohol and ammoniacal liquor mixed solution, take the Ag metallic particles as seed, the TEOS hydrolysis precipitation forms SiO in the metal surface
2Shell, it is high that this preparation method exists experience to require, poor reproducibility, technique is loaded down with trivial details, and products therefrom purity is low, and disposable having high input restricted Ag@SiO
2The practical application of nuclear-shell structured nano-composite material.
Summary of the invention
For the deficiency of existing metal/silica core-shell nano technology of preparing, the present invention is by a kind of Ag@SiO
2The preparation method of nuclear-shell structured nano-composite material, the method favorable reproducibility, products therefrom purity is good, and pattern and size are adjustable, and the preparation facilities requirement is low, and production efficiency is high, and cost is low.
Summary of the invention: it is that template prepares Ag@SiO that the present invention adopts reverse microemulsion process
2Nuclear-shell structured nano-composite material adopts continuous sample-adding, the generation that Ag is nanocrystalline and SiO
2The covering of shell is all completed in a reactor.The Ag@SiO of preparation
2Core-shell material is the pattern rule both, has again considerable material property simultaneously; And described Ag@SiO
2The pattern of core-shell material and size can be regulated easily by changing process conditions.
The term explanation:
Oligo surfactant (Tyloxapol) is the oligomer (TX-100) of isobutyl group phenol polyethenoxy (10) ether, is called for short the TX-100 oligomer, and its average degree of polymerization n is 7, and every two TX-100 monomers are connected by a methylene.But market is bought.
Detailed Description Of The Invention:
Technical scheme of the present invention is as follows:
A kind of Ag@SiO
2The preparation method of nuclear-shell structured nano-composite material comprises the following steps:
(1) prepare reverse micro emulsion as mother liquor with non-ionic surface active agent, oil phase, cosurfactant, wherein, non-ionic surface active agent: oil phase: cosurfactant=4:5～10:0～4 mass ratioes;
Described non-ionic surface active agent is isobutyl group phenol polyethenoxy (10) ether (Triton X-100, TX-100), oligo surfactant (Tyloxapol, average degree of polymerization n is 7), NPE NP8, NPE NP15 or AEO C
16E
10;
Described oil phase is cyclohexane, n-hexane or benzinum;
Described cosurfactant is n-amyl alcohol, n-hexyl alcohol or n-octyl alcohol;
(2) mother liquor of getting step (1) is in reaction bulb, and adding concentration is 0.1～0.2molL
-1Liquor argenti nitratis ophthalmicus, electromagnetic agitation 5-10min at 20～25 ℃ of temperature; Adding concentration is 0.1～1.0molL again
-1Sodium borohydride solution is electromagnetic agitation 25-30min at 20～25 ℃ of temperature; Adding concentration is the ammoniacal liquor of 6.42～26.5wt% again, electromagnetic agitation 5-8min at 20～25 ℃ of temperature; Then, add ethyl orthosilicate (TEOS), at 26 ± 1 ℃ of temperature electromagnetic agitation 20-24 hour, generate Ag@SiO
2Nuclear-shell structured nano-composite material;
The addition of described liquor argenti nitratis ophthalmicus is: mother liquor: liquor argenti nitratis ophthalmicus=3.5～4.5g:200-500 μ l;
The addition of described sodium borohydride solution is: the mol ratio of silver nitrate and sodium borohydride is 0.5～2:1;
The addition of described ammoniacal liquor is: mother liquor: ammoniacal liquor=3.5～4.5g:150～400 μ L;
The addition of described ethyl orthosilicate is 170～400 μ L;
Volume ratio V (the AgNO of described liquor argenti nitratis ophthalmicus and ethyl orthosilicate
3(aq)/TEOS) be 1:1～2;
(3) add acetone to make it phase-splitting in step (2) reaction system, centrifugal 5-10min then, the absolute ethyl alcohol ultrasonic cleaning of gained solid, cleaned solid is dry at 55～65 ℃ of temperature, namely gets Ag@SiO
2The nuclear-shell structured nano-composite material powder.
Preferred according to the present invention, the centrifugal of above-mentioned steps (3) is centrifugal 5min under 8000-10000rmp, and the solid that obtains absolute ethyl alcohol ultrasonic cleaning then centrifugal, is carried out centrifugal-cleaning 2～3 times so repeatedly.
Preferred according to the present invention, the non-ionic surface active agent of step (1): oil phase: cosurfactant=4:7～8:1～4.
Preferred according to the present invention, step (1) isobutyl group phenol polyethenoxy (10) ether (TX-100), cyclohexane, n-hexyl alcohol 4:7.5:1 are in mass ratio prepared reverse micro emulsion as mother liquor.
Preferred according to the present invention, step (1) isobutyl group phenol polyethenoxy (10) ether (TX-100), cyclohexane, n-octyl alcohol 2:4:1 are in mass ratio prepared reverse micro emulsion as mother liquor;
Preferred according to the present invention, step (1) oligo surfactant (Tyloxapol), cyclohexane, n-hexyl alcohol 1:2:1 are in mass ratio prepared reverse micro emulsion as mother liquor;
Preferred according to the present invention, the mol ratio (n (AgNO of the silver nitrate of step (2) and sodium borohydride
3/ NaBH
4)) be 1.5-2, obtain solid Ag@SiO
2Core-shell nanospheres;
Preferred according to the present invention, the mol ratio (n (AgNO of the silver nitrate of step (2) and sodium borohydride
3/ NaBH
4)) be greater than 0.66 less than 1.5, obtain the Ag@SiO of single hole
2Core-shell nanospheres;
Preferred according to the present invention, the mol ratio (n (AgNO of the silver nitrate of step (2) and sodium borohydride
3/ NaBH
4)) be 0.5-0.66, obtain the Ag@SiO of porous
2Core-shell nanospheres.
Ag@SiO of the present invention
2In the preparation method of nuclear-shell structured nano-composite material, raw materials usedly be commercial product.Wherein, described deionized water is three water, and it is pure that the agents useful for same specification is analysis, and described solution all seals lucifuge normal temperature and preserves, and wherein sodium borohydride solution and ammonium hydroxide aqueous solution are take now with the current as good, and all the other solution storage times are no more than a week.Be 0.1～1.0molL with deionized water preparation sodium borohydride solution concentration
-1, ammonium hydroxide aqueous solution concentration is 6.42～26.5%; Liquor argenti nitratis ophthalmicus concentration is 0.1～0.2molL
-1
In preparation method of the present invention, related chemical reaction is as follows:
2AgNO
3+2NaBH
4+6H
2O=2Ag+2NaNO
3+2H
3BO
3+7H
2
Hydrolytic process is:
Hydrolysis: ≡ Si-OR+H
2O=≡ Si-OH+ROH
Dealcoholysis condensation: ≡ Si-OH+ ≡ Si-OR=≡ Si-O-Si ≡+ROH
Dehydrating condensation: ≡ Si-OH+ ≡ Si-OH=≡ Si-O-Si ≡+H
2O
Use the molar ratio of silver nitrate and sodium borohydride by change, obtain the material of different-shape.As the molar ratio (n (AgNO that uses silver nitrate and sodium borohydride
3/ NaBH
4)) greater than 1.5 o'clock, obtain the nanosphere of solid construction; The molar ratio of silver nitrate and sodium borohydride (n (AgNO
3/ NaBH
4)) greater than 0.66 and less than 1.5 o'clock, obtain the nanosphere of single hole structure; The molar ratio of silver nitrate and sodium borohydride (n (AgNO
3/ NaBH
4)) less than 0.66 o'clock, obtain the nanosphere of loose structure.
Material characteristics set forth in the present invention can be tested with following methods:
1, transmission electron microscope (TEM) and high resolution electron microscope (HRTEM).Can know by TEM and HRTEM and show Ag@SiO
2The microscopic appearance of core-shell nano material and size;
2, X-ray diffraction (XRD).Can obtain the composition of institute's synthetic material by X-ray diffraction, material internal atom, molecular structures and form;
3, X-ray photoelectron spectroscopic analysis (XPS).Can obtain qualitative elementary analysis result in institute's synthetic material by X-ray photoelectron spectroscopic analysis.
4, UV-vis absorption spectrum.Can characterize the Ag@SiO of different structure by the UV-vis absorption spectrum
2The optical property of nuclear-shell structured nano-composite material.
5, fourier transform infrared spectroscopy (FTIR).Can characterize the Ag@SiO of different structure by the FTIR spectrogram
2The functional group of nuclear-shell structured nano-composite material.
Ag@SiO of the present invention
2The preparation method's of nuclear-shell structured nano-composite material technical characterstic mainly contains following three aspects:
At first, change the ratio R([H of response parameter water and non-ionic surface active agent
2O]/[Surfactant]) can regulate Ag@SiO
2The size of Ag core in nuclear-shell structured nano-composite material; Secondly, can control the formation speed of hydrogen by the ratio that changes sodium borohydride and silver nitrate, thereby generate the Ag@SiO of solid, single hole or porous
2Nucleocapsid structure; Again, can control Ag@SiO by the addition of regulating TEOS
2SiO in nuclear-shell structured nano-composite material
2The size of shell, thus the Ag@SiO of different-shape, size and character obtained
2Nuclear-shell structured nano-composite material.
It is that template prepares Ag@SiO that the present invention adopts reverse microemulsion process
2Nuclear-shell structured nano-composite material, continuous sample-adding, the generation that Ag is nanocrystalline and SiO
2The covering of shell is all completed in a reactor, and technique is simple, and equipment requirement is low, and production efficiency is high, and cost is low, and product has considerable material character.In the process of sodium borohydride reduction silver nitrate, because reaction speed is very fast, can produce a large amount of hydrogen in system, owing to having little time whole releases, can be wrapped in nucleocapsid structure, thereby increase the porosity of material, can satisfy the requirement of industrial and agricultural production under specified conditions.
Advantage of the present invention is, at above-mentioned Ag@SiO
2In nuclear-shell structured nano-composite material, can be by the kind of reconciliation statement surface-active agent and cosurfactant, the concentration of reducing agent and the addition of TEOS regulate and control Ag@SiO
2The pattern of nuclear-shell structured nano-composite material and size.Like this, the composition of regulation system according to actual needs just is to satisfy different needs.
Description of drawings
Fig. 1 is Ag@SiO in reverse micro emulsion
2The schematic diagram of core-shell nano material forming process.
Fig. 2 is n (AgNO
3/ NaBH
4)=1.5, the volume ratio V (AgNO of silver nitrate and ethyl orthosilicate
3(aq)/TEOS)=1, the Ag@SiO when content of water in system is 12.7%
2The TEM photo of core-shell nano material.
Fig. 3 is n (AgNO
3/ NaBH
4)=1, V (AgNO
3(aq)/TEOS)=2, the Ag@SiO when content of water in system is 16.6%
2(a) TEM photo of core-shell nano material and (b), (c) HR-TEM photo, (c) in illustration be the SEAD figure (SAED) of sample; Photo (d) is this Ag@SiO
2The core-shell nano material is processed through NaOH and is removed SiO
2TEM after shell and (e), (f) HR-TEM photo, (f) in illustration be to remove SiO
2The SAED figure of the sample after shell.
Fig. 4 is n (AgNO
3/ NaBH
4)=0.5, V (AgNO
3(aq)/TEOS)=2, the Ag@SiO when content of water in system is 16.6%
2(a) TEM photo of core-shell nano material and (b) HR-TEM photo.
Fig. 5 is n (AgNO
3/ NaBH
4)=2, V (AgNO
3(aq)/TEOS)=2, the Ag@SiO when content of water in system is 14.2%
2The TEM photo of core-shell nano material.
Fig. 6 is n (AgNO
3/ NaBH
4)=1, V (AgNO
3(aq)/TEOS)=1, the Ag@SiO when content of water in system is 11.1%
2The TEM photo of core-shell nano material.
Fig. 7 is n (AgNO
3/ NaBH
4)=1, V (AgNO
3The Ag@SiO of (aq)/TEOS)=2 o'clock
2The XPS spectrum figure of core-shell nano material; A is the full spectrogram of sample, and B-D is respectively Ag3d, Si2p and the O1s enlarged drawing of sample.Abscissa is that ordinate is relative intensity in conjunction with energy.
Fig. 8 is n (AgNO
3/ NaBH
4)=0.5, V (AgNO
3The Ag@SiO of (aq)/TEOS)=2 o'clock
2The XPS spectrum figure of core-shell nano material; Abscissa is that ordinate is relative intensity in conjunction with energy.
Fig. 9 is (a) SiO
2, (b) Ag@SiO
2, (c) Ag nano material the XRD collection of illustrative plates.
Figure 10 is (a) pure SiO
2, (b) volume ratio V (AgNO
3(aq)/TEOS)=2, n (AgNO
3/ NaBH
4)=1.5, (c) V (AgNO
3(aq)/TEOS)=2, n (AgNO
3/ NaBH
4)=1, (d) V (AgNO
3(aq)/TEOS)=2, n (AgNO
3/ NaBH
4The Ag@SiO of)=0.5 o'clock
2The FTIR spectrogram of core-shell nano material.Abscissa: wave number (cm
-1), ordinate: transmitance (arbitrarily).
Figure 11 is (a) pure SiO
2Nano material, (b) V (AgNO
3(aq)/TEOS)=2, n (AgNO
3/ NaBH
4)=1.5, (c) V (AgNO
3(aq)/TEOS)=2, n (AgNO
3/ NaBH
4)=1 o'clock Ag@SiO
2The UV-vis absorption spectrum of core-shell nano material.Abscissa: wavelength (nm), ordinate: absorb.
Figure 12 is (a) pure SiO
2The Ag@SiO of nano material and (b, c) different structure
2The TGA curve of core-shell nano material.Abscissa: temperature (℃), ordinate: weight (%).
The specific embodiment
The present invention is further elaborated below in conjunction with drawings and Examples.To help to understand by the following description of the embodiments the present invention, but not limit content of the present invention.
With three water respectively compound concentration be 0.2molL
-1Liquor argenti nitratis ophthalmicus, concentration is 0.2molL
-1, 0.8molL
-1Sodium borohydride solution, concentration are 14.2wt% ammonium hydroxide aqueous solution (ammoniacal liquor); For following embodiment 1-3.
The mother liquor of embodiment 1-3: with non-ionic surface active agent TX-100, oil phase cyclohexane, cosurfactant n-hexyl alcohol preparation reverse micro emulsion, TX-100: cyclohexane: n-hexyl alcohol in mass ratio=4:7.5:1.
Embodiment 1: solid Ag@SiO
2The preparation of nuclear-shell structured nano-composite material
Take the 3.91g mother liquor in sample bottle, accurately pipette 255 μ l0.2mol/L AgNO with liquid-transfering gun
3Solution joins in mother liquor, electromagnetic agitation 5min under room temperature; Then accurately pipette 170 μ l0.2mol/L NaBH with liquid-transfering gun
4Solution joins in system, electromagnetic agitation 30min under room temperature; Accurately pipette 170 μ l14.2% ammonia spirits with liquid-transfering gun again, join in system, electromagnetic agitation 5min under room temperature; Accurately pipette 170 μ l TEOS with liquid-transfering gun at last, join in system, electromagnetic agitation 24h at the temperature of 26 ± 1 ℃.Reaction adds a small amount of acetone to make it phase-splitting in reaction system after finishing, and then mixture is moved in centrifuge tube, and centrifugal 5min, obtain solid under 10000rmp.Then use the absolute ethyl alcohol ultrasonic cleaning.Centrifugal and absolute ethyl alcohol ultrasonic cleaning repeats three times.
The centrifugal solid that obtains is dry at 60 ℃ of temperature, namely get solid Ag@SiO
2The nuclear-shell structured nano-composite material powder.Solid Ag@SiO
2Nucleocapsid structure TEM figure as shown in Figure 2; The FTIR spectrogram is as shown in b in accompanying drawing 10; The UV-vis absorption spectrum is as shown in b in accompanying drawing 11.
Embodiment 2: single hole Ag@SiO
2The preparation of nuclear-shell structured nano-composite material
Take the 3.91g mother liquor in sample bottle, accurately pipette 340 μ l0.2mol/L AgNO with liquid-transfering gun
3Solution joins in mother liquor, electromagnetic agitation 5min under room temperature; Then accurately move 340 μ l0.2mol/L NaBH with liquid-transfering gun
4Solution joins in system, electromagnetic agitation 30min under room temperature; Accurately pipette 170 μ l14.2% ammonia spirits with liquid-transfering gun again, join in system, electromagnetic agitation 5min under room temperature; Accurately pipette 170 μ l TEOS with liquid-transfering gun at last, join in system, electromagnetic agitation 24h at the temperature of 26 ± 1 ℃.Reaction adds a small amount of acetone to make it phase-splitting in reaction system after finishing, and then mixture is moved in centrifuge tube, and centrifugal 5min, obtain solid under 10000rmp.Then use the absolute ethyl alcohol ultrasonic cleaning.Centrifugal and absolute ethyl alcohol ultrasonic cleaning repeats three times;
The centrifugal solid that obtains is dry at 60 ℃ of temperature, namely get single hole Ag@SiO
2The nuclear-shell structured nano-composite material powder.Single hole Ag@SiO
2Nucleocapsid structure TEM figure is as shown in the a.b.c. of accompanying drawing 3; XPS spectrum figure as shown in Figure 7; The XRD collection of illustrative plates is as shown in c in accompanying drawing 9; The FTIR spectrogram is as shown in c in accompanying drawing 10; The UV-vis absorption spectrum is as shown in c in accompanying drawing 11.
Embodiment 3: porous Ag@SiO
2The preparation of nuclear-shell structured nano-composite material
Take the 3.91g mother liquor in sample bottle, accurately pipette 340 μ l0.2mol/L AgNO with liquid-transfering gun
3Solution joins in mother liquor, electromagnetic agitation 5min under room temperature; Then accurately pipette 340 μ l0.4mol/L NaBH with liquid-transfering gun
4Solution joins in system, electromagnetic agitation 30min under room temperature; Accurately pipette 170 μ l14.2% ammonia spirits with liquid-transfering gun again, join in system, electromagnetic agitation 5min under room temperature; Accurately pipette 170 μ lTEOS with liquid-transfering gun at last, join in system, electromagnetic agitation 24h at the temperature of 26 ± 1 ℃.Reaction adds a small amount of acetone to make it phase-splitting in reaction system after finishing, and then mixture is moved in centrifuge tube, and centrifugal 5min, obtain solid under 10000rmp.Then use the absolute ethyl alcohol ultrasonic cleaning.Centrifugal and absolute ethyl alcohol ultrasonic cleaning repeats three times;
The centrifugal solid that obtains is dry at 60 ℃ of temperature, namely get porous Ag@SiO
2The nuclear-shell structured nano-composite material powder.Porous Ag@SiO
2Nucleocapsid structure TEM figure as shown in Figure 4; XPS spectrum figure as shown in Figure 8; The FTIR spectrogram is as shown in d in accompanying drawing 10.
Embodiment 4: solid Ag@SiO
2The preparation of nuclear-shell structured nano-composite material
Take the 3.91g mother liquor in sample bottle, accurately pipette 340 μ l0.2mol/L AgNO with liquid-transfering gun
3Solution joins in mother liquor, electromagnetic agitation 5min under room temperature; Then accurately pipette 170 μ l0.2mol/L NaBH with liquid-transfering gun
4Solution joins in system, electromagnetic agitation 30min under room temperature; Accurately pipette 170 μ l14.2% ammonia spirits with liquid-transfering gun again, join in system, electromagnetic agitation 5min under room temperature; Accurately pipette 170 μ lTEOS with liquid-transfering gun at last, join in system, electromagnetic agitation 24h at the temperature of 26 ± 1 ℃.Reaction adds a small amount of acetone to make it phase-splitting in reaction system after finishing, and then mixture is moved in centrifuge tube, and centrifugal 5min, obtain solid under 10000rmp.Then use the absolute ethyl alcohol ultrasonic cleaning.Centrifugal and absolute ethyl alcohol ultrasonic cleaning repeats three times.
The centrifugal solid that obtains is dry at 60 ℃ of temperature, namely get solid Ag@SiO
2The nuclear-shell structured nano-composite material powder.Solid Ag@SiO
2Nucleocapsid structure TEM figure as shown in Figure 5.
Embodiment 5: single hole Ag@SiO
2The preparation of nuclear-shell structured nano-composite material
Take the 3.91g mother liquor in sample bottle, accurately pipette 170 μ l0.2mol/L AgNO with liquid-transfering gun
3Solution joins in mother liquor, electromagnetic agitation 5min under room temperature; Then accurately pipette 170 μ l0.2mol/L NaBH with liquid-transfering gun
4Solution joins in system, electromagnetic agitation 30min under room temperature; Accurately pipette 170 μ l14.2% ammonia spirits with liquid-transfering gun again, join in system, electromagnetic agitation 5min under room temperature; Accurately pipette 170 μ lTEOS with liquid-transfering gun at last, join in system, electromagnetic agitation 24h at the temperature of 26 ± 1 ℃.Reaction adds a small amount of acetone to make it phase-splitting in reaction system after finishing, and then mixture is moved in centrifuge tube, and centrifugal 5min, obtain solid under 10000rmp.Then use the absolute ethyl alcohol ultrasonic cleaning.Centrifugal and absolute ethyl alcohol ultrasonic cleaning repeats three times.
The centrifugal solid that obtains is dry at 60 ℃ of temperature, namely get single hole Ag@SiO
2The nuclear-shell structured nano-composite material powder.Single hole Ag@SiO
2Nucleocapsid structure TEM figure as shown in Figure 6.
Claims (9)
1. Ag SiO
2The preparation method of nuclear-shell structured nano-composite material comprises the following steps:
(1) prepare reverse micro emulsion as mother liquor with non-ionic surface active agent, oil phase, cosurfactant, wherein, non-ionic surface active agent: oil phase: cosurfactant=4:5～10:0～4 mass ratioes;
Described non-ionic surface active agent is isobutyl group phenol polyethenoxy (10) ether (Triton X-100, TX-100), oligo surfactant (Tyloxapol, average degree of polymerization n is 7), NPE NP8, NPE NP15 or AEO C
16E
10;
Described oil phase is cyclohexane, n-hexane or benzinum;
Described cosurfactant is n-amyl alcohol, n-hexyl alcohol or n-octyl alcohol;
(2) mother liquor of getting step (1) is in reaction bulb, and adding concentration is 0.1～0.2molL
-1Liquor argenti nitratis ophthalmicus, electromagnetic agitation 5-10min at 20～25 ℃ of temperature; Adding concentration is 0.1～1.0molL again
-1Sodium borohydride solution is electromagnetic agitation 25-30min at 20～25 ℃ of temperature; Adding concentration is the ammoniacal liquor of 6.42～26.5wt% again, electromagnetic agitation 5-8min at 20～25 ℃ of temperature; Then, add ethyl orthosilicate (TEOS), at 26 ± 1 ℃ of temperature electromagnetic agitation 20-24 hour, generate Ag@SiO
2Nuclear-shell structured nano-composite material;
The addition of described liquor argenti nitratis ophthalmicus is: mother liquor: liquor argenti nitratis ophthalmicus=3.5～4.5g:200-500 μ l;
The addition of described sodium borohydride solution is: the mol ratio of silver nitrate and sodium borohydride is 0.5～2:1;
The addition of described ammoniacal liquor is: mother liquor: ammoniacal liquor=3.5～4.5g:150～400 μ L;
The addition of described ethyl orthosilicate is 170～400 μ L;
Volume ratio V (the AgNO of described liquor argenti nitratis ophthalmicus and ethyl orthosilicate
3(aq)/TEOS) be 1:1～2;
(3) add acetone to make it phase-splitting in step (2) reaction system, centrifugal 5-10min then, the absolute ethyl alcohol ultrasonic cleaning of gained solid, cleaned solid is dry at 55～65 ℃ of temperature, namely gets Ag@SiO
2The nuclear-shell structured nano-composite material powder.
2. Ag@SiO according to claim 1
2The preparation method of nuclear-shell structured nano-composite material is characterized in that, the centrifugal of step (3) is centrifugal 5min under 8000-10000rmp, and the solid that obtains absolute ethyl alcohol ultrasonic cleaning then centrifugal, is carried out centrifugal-cleaning 2～3 times so repeatedly.
3. Ag@SiO according to claim 1
2The preparation method of nuclear-shell structured nano-composite material is characterized in that, the non-ionic surface active agent of step (1): oil phase: cosurfactant=4:7～8:1～4.
4. Ag@SiO according to claim 1
2The preparation method of nuclear-shell structured nano-composite material is characterized in that, step (1) isobutyl group phenol polyethenoxy (10) ether (TX-100), cyclohexane, n-hexyl alcohol 4:7.5:1 are in mass ratio prepared reverse micro emulsion as mother liquor.
5. Ag@SiO according to claim 1
2The preparation method of nuclear-shell structured nano-composite material is characterized in that, step (1) isobutyl group phenol polyethenoxy (10) ether (TX-100), cyclohexane, n-octyl alcohol 2:4:1 are in mass ratio prepared reverse micro emulsion as mother liquor.
6. Ag@SiO according to claim 1
2The preparation method of nuclear-shell structured nano-composite material is characterized in that, step (1) oligo surfactant (Tyloxapol), cyclohexane, n-hexyl alcohol 1:2:1 are in mass ratio prepared reverse micro emulsion as mother liquor.
7. Ag@SiO according to claim 1
2The preparation method of nuclear-shell structured nano-composite material is characterized in that, the mol ratio (n (AgNO of the silver nitrate of step (2) and sodium borohydride
3/ NaBH
4)) be 1.5-2, obtain solid Ag@SiO
2Core-shell nanospheres.
8. Ag@SiO according to claim 1
2The preparation method of nuclear-shell structured nano-composite material is characterized in that, the mol ratio (n (AgNO of the silver nitrate of step (2) and sodium borohydride
3/ NaBH
4)) be greater than 0.66 less than 1.5, obtain the Ag@SiO of single hole
2Core-shell nanospheres.
9. Ag@SiO according to claim 1
2The preparation method of nuclear-shell structured nano-composite material is characterized in that, the mol ratio (n (AgNO of the silver nitrate of step (2) and sodium borohydride
3/ NaBH
4)) be 0.5-0.66, obtain the Ag@SiO of porous
2Core-shell nanospheres.
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