CN100482385C - Method for preparing silver/silicon dixoide nucleocapsid structure nano particles - Google Patents
Method for preparing silver/silicon dixoide nucleocapsid structure nano particles Download PDFInfo
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- CN100482385C CN100482385C CNB200710118942XA CN200710118942A CN100482385C CN 100482385 C CN100482385 C CN 100482385C CN B200710118942X A CNB200710118942X A CN B200710118942XA CN 200710118942 A CN200710118942 A CN 200710118942A CN 100482385 C CN100482385 C CN 100482385C
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Abstract
A preparation method of Ag/SiO2 nucleocapsid structure nanoparticles belongs to particle preparation field. Taking AgNO3 as material and hexadecyl trimethyl ammonium bromide as surfactant, the invention prepares Ag nanoparticals by oxidation-reduction reaction in solution under a certain temperature. Reducer for reducing AgNO3 is hydrazinehydrate and ascorbic acid. Based on the prepared Ag nanoparticals, add ethanol and take TEOS as a source of SiO2 to prepare sol solution with SiO2 wrapping Ag nanoparticals. The method has simple operation and low cost. The prepared particles have distinct nucleocapsid structure, uniform granularity and good dispersibility. It has many application prospects in biology sterilization, chemistry and optical materials etc.
Description
Technical field
The invention belongs to the preparation of nanoparticles field, be specifically related to a kind of method for preparing silver/silicon dixoide nucleocapsid structure nano particles
Background technology
Nano material particularly noble metal nanometer material causes people's extensive interest because it has the unusual characteristic that is different from traditional material at aspects such as mechanics, electricity, calorifics, optics, catalysis.A kind of especially widely used metal material of nano-Ag particles wherein, it more and more is subjected to people's attention in performance and the potential application that aspects such as catalytic reaction, optics conduction, surface modification, biochemistry application show.But because under nano-scale, there is higher surface energy in nano particle, has the tendency of reuniting easily in medium, causes bad dispersibility, has limited the application of nano material greatly.Recently, by at the surfaces of metal nanoparticles coated polymer, surfactant and titanium dioxide etc. has attracted researcher's sight.More existing wrap up the method report of silver-colored particle with silica, (Langmuir 1998,14 for T.Ung, et al, 3740-3748) with AgClO as T.Ung etc.
4Be the nano-Ag particles of feedstock production, C.Graf etc. (Langmuir 2003,19 for C.Graf, et al, and in article 6693-6700), be that coupling agent wraps up silica with pvp, but all exist cost of material more expensive relatively, and complex process, dangerous big.And up to the present, the preparation of these nano particles mainly all concentrates on the stage of low concentration, and is unfavorable for large-scale industrial production.
Summary of the invention
At the deficiencies in the prior art, the object of the present invention is to provide a kind of single dispersion that possesses, concentration is at 100-400ppm, and preparation technology is simple, the preparation method of handling safety, silica parcel silver nano-grain that cost is low, further wishes to solve the problem that granule size is controlled, pattern is controlled.
The present invention is under the magnetic agitation condition, adds reducing agent and obtain nano-Ag particles in liquor argenti nitratis ophthalmicus, and directly add the nano-Ag particles that ethyl orthosilicate obtains the silica parcel in this solution.
A kind of method for preparing silver/silicon dixoide nucleocapsid structure nano particles is characterized in that, may further comprise the steps:
1) the surfactant softex kw being dissolved in water, to form concentration be the aqueous solution of 1mmol/L-4mmol/L, and according to the difference of reducing agent, the addition sequence of decision reducing agent and silver nitrate:
When reducing agent is hydrazine hydrate, in the aqueous solution of surfactant, add excessive hydrazine hydrate earlier, drip liquor argenti nitratis ophthalmicus again; When reducing agent is ascorbic acid, in the aqueous solution of surfactant, add liquor argenti nitratis ophthalmicus earlier, drip excessive ascorbic acid again;
The concentration of silver nitrate in solution is 1.25mmol/L-5mmol/L, and silver nitrate and reducing agent reaction time are controlled to be 3-30 minute;
Dropping sodium was adjusted into 6-11 with reacting liquid pH value when 2) dropping ammonia or reducing agent were ascorbic acid when reducing agent is hydrazine hydrate;
3) in above-mentioned reactant liquor, add absolute ethyl alcohol, the consumption of absolute ethyl alcohol is 1/6 to 1/3 of an above-mentioned reactant liquor volume, adds ethyl orthosilicate then in mixed solution, continues to stir, and obtains silver/silicon dixoide nucleocapsid structure nano particles.
The concentration of hydrazine hydrate in solution is 0.001mol/L-0.0025mol/, and ascorbic acid concentrations is 5/6 of a silver nitrate concentration.
In above-mentioned steps, reaction is all carried out under the condition of magnetic agitation, all is that the redox reaction by silver nitrate and reducing agent obtains nano-Ag particles.
Above-mentioned steps 2) in, silver nitrate and reducing agent reaction regular hour, the time, too short reaction was incomplete, and oversize nano-Ag particles of time is grown up easily, and the reaction time is 3-30 minute.The preferred reaction time is 5 minutes-10 minutes.
The time of continuing above-mentioned steps 3) to stir is 1-24 hour.
Above-mentioned steps 2) in, the volume of reconciling the used ammoniacal liquor of pH value is 1/100-/40 of all reactant liquor volumes in the step 1).The ammoniacal liquor mass percent concentration is 25%.
Among the present invention, what surfactant adopted is the cetyl trimethyl ammonia bromide, the characteristic of its cationic surfactant can be adhered to it on the electronegative nano-Ag particles in surface, improve the dispersiveness of nano-Ag particles, its concentration is too low can't to play effect, can strengthen intergranular adhesion degree and concentration is too high
Among the present invention, the concentration of silver nitrate in mixed solution is up to 5mmol/L, and minimum is 1.25mmol/L.
The ratio of TEOS and silver nitrate is bigger to the pattern influence of particle among the present invention, and the TEOS amount of substance of adding is the 1/5-2.5/1 of reaction silver nitrate amount of substance.Suitable ratio helps to improve the covered effect of particle.
In sum, can find out that the pointed method technology of the present invention is simple, not relate to hazardous environments such as dangerous material and high pressure in all operations, handling safety, cost is lower, and can access the silver/silicon dixoide nucleocapsid structure nano particles of many concentration monodispersity, provide the foundation for application such as further biochemistry, anti-biotic material, surface modification.
Description of drawings
For further introducing the present invention, show used description of drawings is as follows by embodiment:
Fig. 1 is the transmission electron microscope photo of the nuclear shell structure nano particle of reducing agent preparation with the ascorbic acid, and silver concentration is 2.5mmol/L.
Fig. 2 is the transmission electron microscope photo of the nuclear shell structure nano particle of reducing agent preparation with the ascorbic acid, and silver concentration is 5mmol/L.
Fig. 3 is that the nuclear shell structure nano particle of reducing agent preparation is at 100,000 times transmission electron microscope photo with the hydrazine hydrate.
Fig. 4 is reducing agent with the hydrazine hydrate, is the transmission electron microscope photo of 100,000 times of the nuclear shell structure nano particles that prepare under reactant liquor volume 1/3 condition in amount of alcohol added.
Fig. 5 is reducing agent with the hydrazine hydrate, and ammoniacal liquor and ratio are the transmission electron microscope photo of 100,000 times of the nuclear shell structure nano particles that prepare under 1/40 condition.
Fig. 6 is reducing agent with the hydrazine hydrate, and the ethyl orthosilicate amount of substance is under the condition of silver nitrate consumption 20%, the transmission electron microscope photo that the nuclear shell structure nano particle of preparation is 50,000 times.
Fig. 7 is the nuclear shell structure nano particle grain size distribution figure of reducing agent preparation with the ascorbic acid, and silver concentration is 2.5mol/L
The XRD figure of the preparation particle of Fig. 8 embodiment 2.
The UV absorption figure of the preparation particle of Fig. 9 embodiment 2.
The specific embodiment
0.4mmolg cetyl trimethyl ammonia bromide is dissolved in the 180ml water, add silver nitrate, make that silver nitrate concentration is 2.5mmol/L in the whole solution, stir after 1 minute, slowly at the uniform velocity the adding mixed liquor, regulate the pH value with sodium hydroxide solution is 6 to the ascorbic acid (0.417mmol) with 20ml after water-soluble, react after 10 minutes, add 50ml ethanol, drip the 0.5ml ethyl orthosilicate, continue to stir after 3 hours and leave standstill.By electron microscopic observation, as shown in Figure 1, product particle is even, and concentration is 200ppm, and average grain diameter is at 56nm, as shown in Figure 7.
Embodiment 2
0.8mmol the cetyl trimethyl ammonia bromide is dissolved in the 180ml water, add silver nitrate, make that silver nitrate concentration is 5mmol/L in the whole solution, stir after 1 minute, the ascorbic acid (0.83mmol) with 20ml after water-soluble slowly at the uniform velocity the adding mixed liquor, is regulated pH value to 8 with sodium hydroxide solution, react after 10 minutes, add 50ml ethanol, drip the 1ml ethyl orthosilicate, continue to stir after 3 hours and leave standstill.Change dosage of surfactant, and behind the silver nitrate concentration, passing through electron microscopic observation, as shown in Figure 2, dispersiveness does not significantly decrease, and product particle is even, concentration is 400ppm, and the average grain diameter that is approximately the galactic nucleus of 16-22nm and whole particle is about 50nm.
Embodiment 3
2.5ml hydrazine hydrate (0.1mol/L) is splashed in the aqueous solution that contains 0.2mmol cetyl trimethyl ammonia bromide, stir after 2 minutes, at the uniform velocity splash into liquor argenti nitratis ophthalmicus, make that silver nitrate concentration is 1.25mmol/L in the whole solution, continue to stir 7 minutes, add 2ml ammoniacal liquor and 50ml ethanolic solution, the pH value is 10, continue reaction after 1 minute, add the 0.25ml ethyl orthosilicate.Continue to stir after 2 hours and leave standstill.Through electron microscopic observation, as shown in Figure 3, particle favorable dispersibility, and epigranular, concentration is 100ppm, and the galactic nucleus size is between 6-12nm, and particle diameter is between 35-50nm.
Embodiment 4
Operating parameter is similar to embodiment 3, and the volume that different is adds ethanol is 66ml.With electron microscopic observation, as shown in Figure 4, though product still shows as spherical nucleocapsid particles structure, the particle that has coenocytism in the obvious shell increases, and silver-colored particle increases in the nuclear, and concentration is 100ppm.
Embodiment 5
Operating parameter is similar to embodiment 3, and the volume that different is adds ethanol is 33ml.By observing, the silver particles particle obviously increases, and coupling increases, and nucleocapsid structure has not been clearly, and concentration is 100ppm.
Embodiment 6
2ml hydrazine hydrate (0.1mol/L) is splashed in the aqueous solution that contains 0..2mmol cetyl trimethyl ammonia bromide, stir after 2 minutes, at the uniform velocity splash into) liquor argenti nitratis ophthalmicus, make that silver nitrate concentration is 1.25mmol/L in the whole solution, continue to stir 5 minutes, add 5ml ammoniacal liquor and 50ml ethanolic solution, the pH value is 11, continue reaction after 1 minute, add the 0.25ml ethyl orthosilicate.Continue to stir after 1 hour and leave standstill. with electron microscopic observation, as shown in Figure 5, and silver-colored even particle size, about 10nm,, concentration is 100ppm, nucleocapsid structure is obvious.
Embodiment 7
5ml hydrazine hydrate (0.1mol/L) is splashed in the aqueous solution that contains 0.2mmol cetyl trimethyl ammonia bromide, stir after 2 minutes, at the uniform velocity splash into liquor argenti nitratis ophthalmicus, make that silver nitrate concentration is 2.5mmol/L in the whole solution, continue to stir 5 minutes, add 5ml ammoniacal liquor and 66.7ml ethanolic solution, the pH value is 11, continue reaction after 1 minute, add the 0.038ml ethyl orthosilicate.Continuing reaction left standstill after 24 hours. and from the Electronic Speculum result, as shown in Figure 6, owing to reduced the consumption of ethyl orthosilicate, though particle still has dispersiveness preferably, the nucleocapsid structure of particle has not been very obvious, and concentration is 200ppm.
Fig. 8 is the XRD photo of the prepared particle of embodiment 2, can clearly see (111) of silver-colored particle above, (200), (220), and the characteristic absorption peak of (311) face, and silica does not have tangible absworption peak, illustrates that silica is wrapped in silver-colored particle surface and exists with amorphous state.
The UV absorption figure of Fig. 9 embodiment 2 prepared particles.A is the UV absorption of simple substance silver, and b is the UV absorption behind the parcel silica.Can see that the red shift of an absworption peak is arranged behind the parcel, this is caused that by surface parcel silica this has verified that from the another side silver-colored particle surface has silica to exist really.
Claims (2)
1. a method for preparing silver/silicon dixoide nucleocapsid structure nano particles is characterized in that, may further comprise the steps:
1) the surfactant softex kw being dissolved in water formation concentration is the aqueous solution of 1mmol/L-4mmol/L,
In the aqueous solution of surfactant, add excessive reducing agent hydrazine hydrate earlier, drip liquor argenti nitratis ophthalmicus again; Make that the concentration of silver nitrate in whole solution is 1.25mmol/L-5mmol/L, silver nitrate and reducing agent reaction time are controlled to be 3-30 minute;
2) dropping ammonia is adjusted into 6-11 with reacting liquid pH value;
3) add absolute ethyl alcohol, the consumption of absolute ethyl alcohol is a step 2) in the reactant liquor volume 1/6 to 1/3, in mixed solution, add ethyl orthosilicate then, add the 1/5-5/2 of the consumption of tetraethoxysilance for the silver nitrate amount of substance of adding, continue to stir 1 hour by 24 hours, obtain silver/silicon dixoide nucleocapsid structure nano particles.
2. a method for preparing silver/silicon dixoide nucleocapsid structure nano particles is characterized in that, may further comprise the steps:
1) the surfactant softex kw being dissolved in water formation concentration is the aqueous solution of 1mmol/L-4mmol/L,
Earlier in the aqueous solution of surfactant, add liquor argenti nitratis ophthalmicus, drip excessive reducing agent ascorbic acid again; Make that the concentration of silver nitrate in whole solution is 1.25mmol/L-5mmol/L, silver nitrate and reducing agent reaction time are controlled to be 3-30 minute;
2) dropping sodium is adjusted into 6-11 with reacting liquid pH value;
3) add absolute ethyl alcohol, the consumption of absolute ethyl alcohol is a step 2) in the reactant liquor volume 1/6 to 1/3, in mixed solution, add ethyl orthosilicate then, add the 1/5-5/2 of the consumption of tetraethoxysilance for the silver nitrate amount of substance of adding, continue to stir 1 hour by 24 hours, obtain silver/silicon dixoide nucleocapsid structure nano particles.
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| CN101816302A (en) * | 2010-04-06 | 2010-09-01 | 南京奥特高科技有限公司 | Nuclear shell structure intelligent disinfectant containing silver |
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