CN103143721B - Preparation method of Ag@SiO2 core-shell structure nano composite - Google Patents

Preparation method of Ag@SiO2 core-shell structure nano composite Download PDF

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CN103143721B
CN103143721B CN201310082247.8A CN201310082247A CN103143721B CN 103143721 B CN103143721 B CN 103143721B CN 201310082247 A CN201310082247 A CN 201310082247A CN 103143721 B CN103143721 B CN 103143721B
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CN103143721A (en
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辛霞
卢杭
徐桂英
任华英
鞠焕凤
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Shandong University
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Shandong University
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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

A kind of Ag@SiO 2the preparation method of nuclear-shell structured nano-composite material
Technical field
The present invention relates to a kind of Ag@SiO 2the preparation method of nuclear-shell structured nano-composite material, belongs to 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 new function composite, has important application in fields such as photonic bandgap material, microwave absorbing material, catalyst and biologies.Nuclear-shell structured nano-composite material, its inside and outside enrichment heterogeneity respectively, demonstrates special bilayer or sandwich construction.Function by core and shell is compound and complementary, modulates 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 at least higher 20 times than common silver, and therefore, Nano Silver, because the heat of its uniqueness, optical, electrical, magnetic, catalysis and the characteristic such as responsive receive people's concern, is 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.But the research of the optical property to silver particles is mainly confined in glass or aqueous solution medium conventionally, in this case, the absworption peak that the surface plasma body resonant vibration of silver particles causes, in 400nm left and right, 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.Conventionally the SiO adopting in functional material 2mostly be unformed shape, this amorphous Si O 2there is good light sensitivity and the wide spectrum transparency.Therefore, amorphous SiO 2in the Related products such as optical, electrical components and parts, low reflectance coating, insulating barrier, diffusion blocking film, have a wide range of applications.It should be noted that and work as amorphous SiO 2while carrying out some special doping treatment, the optical property of himself will obtain significant raising or change, thereby, amorphous Si O 2also there is 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 2nucleocapsid structure material is by the continuous amorphous SiO that is distributed in of nanoscale Ag uniform particles disperse 2among matrix, effectively control the reunion of Ag nano particle and grown up, simultaneously amorphous SiO 2be wrapped in Ag nano particle around, improved significantly the stability of Ag nano particle, and improved the surface characteristic of Ag nano particle, thereby make the practicality of Ag nano particle obtain greatly lifting.
The preparation method of metal/silica core-shell nano is mainly liquid phase deposition, and in absolute ethyl alcohol and ammoniacal liquor mixed solution, taking Ag metallic particles as seed, TEOS hydrolysis precipitation forms SiO in 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 preparation facilities requirement is low, and production efficiency is high, and cost is low.
Summary of the invention: it is that template is prepared 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 all completes in a reactor.The Ag@SiO of preparation 2core-shell material is pattern rule both, has again considerable material property simultaneously; And described Ag@SiO 2the pattern of core-shell material and size can regulate easily by changing process conditions.
Term explanation:
Oligo surfactant (Tyloxapol), is the oligomer (TX-100) of isobutyl group phenol polyethenoxy (10) ether, is called for short TX-100 oligomer, and its average degree of polymerization n is 7, and every two TX-100 monomers are connected by a methylene.Can buy in market.
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 ratio;
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 DEG C of temperature; Adding concentration is 0.1～1.0molL again -1sodium borohydride solution is electromagnetic agitation 25-30min at 20～25 DEG C of temperature; Adding concentration is the ammoniacal liquor of 6.42～26.5wt% again, electromagnetic agitation 5-8min at 20～25 DEG C of temperature; Then, add ethyl orthosilicate (TEOS), electromagnetic agitation 20-24 hour at 26 ± 1 DEG C of temperature, generates 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) in step (2) reaction system, add acetone to make it phase-splitting, then centrifugal 5-10min, the absolute ethyl alcohol ultrasonic cleaning of gained solid, cleaned solid is dry at 55～65 DEG C of temperature, obtains Ag@SiO 2nuclear-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 obtaining 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 in mass ratio 4:7.5:1 are 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 in mass ratio 2:4:1 are prepared reverse micro emulsion as mother liquor;
Preferred according to the present invention, step (1) oligo surfactant (Tyloxapol), cyclohexane, n-hexyl alcohol in mass ratio 1:2:1 are 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 less than 1.5 for being greater than 0.66, 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, be raw materials usedly commercial product.Wherein, described deionized water is three water, and it is pure that 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 taking now with the current as good, and all the other solution storage times are no more than one week.Preparing sodium borohydride solution concentration by deionized water is 0.1～1.0molL -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.When using the molar ratio (n (AgNO of silver nitrate and sodium borohydride 3/ NaBH 4)) be greater than at 1.5 o'clock, obtain the nanosphere of solid construction; Molar ratio (n (the AgNO of silver nitrate and sodium borohydride 3/ NaBH 4)) be greater than 0.66 and be less than at 1.5 o'clock, obtain the nanosphere of single hole structure; Molar ratio (n (the AgNO of silver nitrate and sodium borohydride 3/ NaBH 4)) be less than at 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 and show Ag@SiO by TEM and HRTEM 2the microscopic appearance of core-shell nano material and size;
2, X-ray diffraction (XRD).Can obtain the composition of synthesized material by X-ray diffraction, the Structure and form of material internal atom, molecule;
3, X-ray photoelectron spectroscopic analysis (XPS).Can obtain the qualitative elementary analysis result in synthesized material by X-ray photoelectron spectroscopic analysis.
4, UV-vis absorption spectrum.Can characterize the Ag@SiO of different structure by 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 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:
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 that regulates 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 is prepared 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 all completes 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 system, in the process of sodium borohydride reduction silver nitrate, because reaction speed is very fast, can produce a large amount of hydrogen, owing to having little time whole release, can be wrapped in nucleocapsid structure, thereby increase the porosity of material, can meet 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 just composition of regulation system according to actual needs, to meet different needs.
Brief description of the 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, 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, 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 2core-shell nano material is processed and is removed SiO through NaOH 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, 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, 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, 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 3(aq)/TEOS)=Ag@the SiO of 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 3(aq)/TEOS)=Ag@the SiO of 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 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 (DEG C), ordinate: weight (%).
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is further elaborated.To contribute 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 is 14.2wt% ammonium hydroxide aqueous solution (ammoniacal liquor); For following examples 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 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; Finally accurately pipette 170 μ l TEOS with liquid-transfering gun, join in system electromagnetic agitation 24h at the temperature of 26 ± 1 DEG C.After reaction finishes, in reaction system, add a small amount of acetone to make it phase-splitting, then mixture is moved in centrifuge tube, under 10000rmp, centrifugal 5min, obtains solid.Then use absolute ethyl alcohol ultrasonic cleaning.Centrifugal and absolute ethyl alcohol ultrasonic cleaning repeats three times.
The centrifugal solid obtaining is dry at 60 DEG C of temperature, obtain solid Ag@SiO 2nuclear-shell structured nano-composite material powder.Solid Ag@SiO 2nucleocapsid structure TEM schemes as shown in Figure 2; FTIR spectrogram is as shown in b in accompanying drawing 10; 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 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; Finally accurately pipette 170 μ l TEOS with liquid-transfering gun, join in system electromagnetic agitation 24h at the temperature of 26 ± 1 DEG C.After reaction finishes, in reaction system, add a small amount of acetone to make it phase-splitting, then mixture is moved in centrifuge tube, under 10000rmp, centrifugal 5min, obtains solid.Then use absolute ethyl alcohol ultrasonic cleaning.Centrifugal and absolute ethyl alcohol ultrasonic cleaning repeats three times;
The centrifugal solid obtaining is dry at 60 DEG C of temperature, obtain single hole Ag@SiO 2nuclear-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; XRD collection of illustrative plates is as shown in c in accompanying drawing 9; FTIR spectrogram is as shown in c in accompanying drawing 10; 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 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; Finally accurately pipette 170 μ lTEOS with liquid-transfering gun, join in system, electromagnetic agitation 24h at the temperature of 26 ± 1 DEG C.After reaction finishes, in reaction system, add a small amount of acetone to make it phase-splitting, then mixture is moved in centrifuge tube, under 10000rmp, centrifugal 5min, obtains solid.Then use absolute ethyl alcohol ultrasonic cleaning.Centrifugal and absolute ethyl alcohol ultrasonic cleaning repeats three times;
The centrifugal solid obtaining is dry at 60 DEG C of temperature, obtain porous Ag@SiO 2nuclear-shell structured nano-composite material powder.Porous Ag@SiO 2nucleocapsid structure TEM schemes as shown in Figure 4; XPS spectrum figure as shown in Figure 8; 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 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; Finally accurately pipette 170 μ lTEOS with liquid-transfering gun, join in system, electromagnetic agitation 24h at the temperature of 26 ± 1 DEG C.After reaction finishes, in reaction system, add a small amount of acetone to make it phase-splitting, then mixture is moved in centrifuge tube, under 10000rmp, centrifugal 5min, obtains solid.Then use absolute ethyl alcohol ultrasonic cleaning.Centrifugal and absolute ethyl alcohol ultrasonic cleaning repeats three times.
The centrifugal solid obtaining is dry at 60 DEG C of temperature, obtain solid Ag@SiO 2nuclear-shell structured nano-composite material powder.Solid Ag@SiO 2nucleocapsid structure TEM schemes as shown in Figure 5.
Embodiment 5: single hole Ag@SiO 2the preparation of nuclear-shell structured nano-composite material
Take 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; Finally accurately pipette 170 μ lTEOS with liquid-transfering gun, join in system, electromagnetic agitation 24h at the temperature of 26 ± 1 DEG C.After reaction finishes, in reaction system, add a small amount of acetone to make it phase-splitting, then mixture is moved in centrifuge tube, under 10000rmp, centrifugal 5min, obtains solid.Then use absolute ethyl alcohol ultrasonic cleaning.Centrifugal and absolute ethyl alcohol ultrasonic cleaning repeats three times.
The centrifugal solid obtaining is dry at 60 DEG C of temperature, obtain single hole Ag@SiO 2nuclear-shell structured nano-composite material powder.Single hole Ag@SiO 2nucleocapsid structure TEM schemes as shown in Figure 6.

Claims (6)

1. the Ag SiO that pattern is adjustable 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 ratio;
Described non-ionic surface active agent is isobutyl group phenol polyethenoxy (10) ether (TX-100), the Tyloxapol that 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 ~ 0.2mol.L -1liquor argenti nitratis ophthalmicus, electromagnetic agitation 5-10min at 20 ~ 25 DEG C of temperature; Adding concentration is 0.1 ~ 1.0mol.L again -1sodium borohydride solution is electromagnetic agitation 25-30min at 20 ~ 25 DEG C of temperature; Adding concentration is the ammoniacal liquor of 6.42 ~ 26.5wt% again, electromagnetic agitation 5-8min at 20 ~ 25 DEG C of temperature; Then, add ethyl orthosilicate, electromagnetic agitation 20-24 hour at 26 ± 1 DEG C of temperature, generates 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;
The volume ratio of described liquor argenti nitratis ophthalmicus and ethyl orthosilicate v(AgNO 3(aq)/TEOS) be 1:1 ~ 2;
When the mol ratio of silver nitrate and sodium borohydride is 1.5-2, obtain solid Ag@SiO 2core-shell nanospheres; Or,
Be less than 1.5 when the mol ratio of silver nitrate and sodium borohydride is greater than 0.66, obtain the Ag@SiO of single hole 2core-shell nanospheres; Or,
When the mol ratio of silver nitrate and sodium borohydride is 0.5-0.66, obtain the Ag@SiO of porous 2core-shell nanospheres;
(3) in step (2) reaction system, add acetone to make it phase-splitting, then centrifugal 5-10 min, the absolute ethyl alcohol ultrasonic cleaning of gained solid, cleaned solid is dry at 55 ~ 65 DEG C of temperature, obtains Ag@SiO 2nuclear-shell structured nano-composite material powder.
2. the adjustable Ag@SiO of a kind of pattern 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 8000-10000r/min, and the solid obtaining absolute ethyl alcohol ultrasonic cleaning, then centrifugal, is carried out centrifugal-cleaning 2 ~ 3 times so repeatedly.
3. the adjustable Ag@SiO of a kind of pattern 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. the adjustable Ag@SiO of a kind of pattern 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 in mass ratio 4:7.5:1 are prepared reverse micro emulsion as mother liquor.
5. the adjustable Ag@SiO of a kind of pattern 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 in mass ratio 2:4:1 are prepared reverse micro emulsion as mother liquor.
6. the adjustable Ag@SiO of a kind of pattern according to claim 1 2the preparation method of nuclear-shell structured nano-composite material, is characterized in that, Tyloxapol that step (1) is 7 with average degree of polymerization n, cyclohexane, n-hexyl alcohol in mass ratio 1:2:1 preparation reverse micro emulsion as mother liquor.
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