CN102896327A - Method for preparing cubic crystal type nano-silver material by utilizing oil-water interface method of oil-soluble protective agent - Google Patents
Method for preparing cubic crystal type nano-silver material by utilizing oil-water interface method of oil-soluble protective agent Download PDFInfo
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- CN102896327A CN102896327A CN2012104225931A CN201210422593A CN102896327A CN 102896327 A CN102896327 A CN 102896327A CN 2012104225931 A CN2012104225931 A CN 2012104225931A CN 201210422593 A CN201210422593 A CN 201210422593A CN 102896327 A CN102896327 A CN 102896327A
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Abstract
The invention relates to a method for preparing a cubic crystal type nano-silver material by utilizing an oil-water interface method of an oil-soluble protective agent. The method comprises the following steps: (1) dissolving silver stearate in cyclohexane at 80 DEG C, adding a surface active agent, and stirring till a solution is clear and transparent, thereby obtaining a silver precursor; dissolving sodium borohydride in deionized water at room temperature and uniformly stirring, thereby obtaining a boron hydrogen base precursor; and (2) adding the boron hydrogen base precursor to the silver precursor, electrically stirring an upper-layer oil phase at 80 DEG C, magnetically stirring a lower-layer water phase, separating and cleaning the obtained products, and finally drying the products, thereby obtaining the cubic crystal type nano-silver material. According to the method provided by the invention, the operation is simple, the reaction condition is mild, the obtained cubic crystal type nano-silver material grains are uniformly dispersed and are stable, and the application prospect is excellent.
Description
Technical field
The invention belongs to the preparation field of nano silver material, particularly the method for the protectant preparing cubic crystal nano silver material by oil-water interface of described a kind of oil-soluble.
Background technology
Recently, the researcher not only to prepare single dispersion, have good uniformity, the research of nano-Ag particles that size is controlled has keen interest, and they have also promoted a class to the application of Nano Silver.Oil-soluble nano-Ag particles purposes is very extensive, for example, and can be with the laboratory materials of oil-soluble nano-Ag particles as each large colleges and universities and research institute; Be used for nonpolar and than low pole solution catalysts; Be used for low pole plastic master batch spiral shell and extrude antibacterial additives; Be used for nano-silver conductive printing ink, conducting resinl, plated film, stealth material etc.Meanwhile, the range of application of water-soluble nano silver particle also is very extensive.Materials Academy professor Zhu Meifang of Donghua University unites the independent research of other institutes and goes out the Nano Silver antimicrobial socks, can effectively treat beriberi, and has reached industrialization, and annual return reaches more than 900 ten thousand.We can connect biological micromolecule on the Nano Silver surface that surfactant coats, and carry out the fields such as catalytic reaction in biomarker, biological monitoring, medicament transport and the aqueous solution.Following research direction will be more synthetic compound nano particle, for example Ag-TiO
2, Ag-Fe
3O
4, Ag-ZnS, Ag-NaYF
4Deng.The character exclusive silver nano-grain combines with the character of other nano particles, and purport is in both common advantages of performance, for example Ag-TiO
2The effect of existing double sterilization can be done again catalyst and degraded macromolecular pollutant; Ag-Fe
3O
4Both had the magnetic positioning action, can be applied to the medicament transport aspect, can carry out sterilization etc. at the drug effect position again simultaneously.
The method for preparing nano silver material commonly used mainly contains hydro-thermal method and microemulsion method at present.Lower and the easy reunion of the particle purity of hydro-thermal method inconvenient operation, preparation, granularity is wayward, and grain diameter is larger, and the product loss is many, and output is lower.The synthetic nano material of microemulsion method has the character of a lot of excellences, but synthetic output is relatively low, and crystallinity is relatively poor.The oil-water interfaces method refers to that the raw material of reactant is in respectively oil phase and aqueous phase, forms the fabulous lipophilic nano particle of the less uniformity of particle diameter at oil-water interface under the lower temperature; Then after nano particle is coated by surfactant under three kinds of surface tension (γ oil is solid, γ profit and γ water solid) and concentration diffusion (because that the Action of Gravity Field of particle affects is very little, can ignore), pull in the upper oil phase, and good dispersion and energy preservation steady in a long-term in oil phase.The oil-water interfaces method has the reaction condition gentleness, and is simple to operate, and particle diameter is controlled, and product purity is high, and productive rate is high, good crystallinity, and good dispersion, particle diameter is little, and cost is low, the advantage that efficient is high.2008, Zhou Xingping etc. adopted oil-water interfaces method [Zhou Xingping etc., Donghua University's journal: natural science edition, 2008,35 (4): 441-444], success synthesize the CdS quantum dot, the CdS quantum dot quantum efficiency of preparing is high, narrow diameter distribution, monodispersity is good, and synthetic method is simple, and temperature requirement is low, can produce in a large number, cost is less.2010, Zhou Xingping etc. adopt again oil-water interfaces method [Zhou Xingping etc., nanosecond science and technology; 2010,12:Vol7, No.6], success synthesize ZnS quantum dot, and some rare metals that mix, fluorescence property is good, is a kind of good semi-conducting material.
Summary of the invention
Technical problem to be solved by this invention provides the method for the protectant preparing cubic crystal nano silver material by oil-water interface of a kind of oil-soluble; the method is simple to operate, reaction condition is gentle; the cubic crystal type nano silver particle that obtains is uniformly dispersed, stablizes, and has a good application prospect.
The method of the protectant preparing cubic crystal nano silver material by oil-water interface of a kind of oil-soluble of the present invention comprises:
(1) silver stearate is dissolved in the cyclohexane under 80 ℃, adds surfactant, be stirred to the solution clear and get silver-colored presoma; Sodium borohydride is dissolved in the deionized water at normal temperatures, and boron hydrogen root presoma stirs to get;
(2) above-mentioned sodium borohydride presoma is joined in the above-mentioned silver-colored presoma, in 80 ℃ of lower upper oil phase electric stirrings, lower floor's water magnetic agitation, the product that obtains is carried out separating, washing, at last product is drying to obtain the cubic crystal type nano ag material.
Surfactant in the described step (1) is zinc stearate, cetylamine and lauryl amine.
The concentration of silver stearate is 0.025-0.0375M in the middle cyclohexane of described step (1).
The concentration 0.075-0.1M of sodium borohydride aqueous solution in the described step (1);
The oil phase that contains silver stearate and oleic acid in the described step (2) and the water volume ratio of sodium borohydride are 1:1.
The speed that sodium borohydride in the described step (2) adds in the cyclohexane solution is 160min/h.
Mixing time in the described step (2) is 2-3h.
Separating, washing in the described step (2) is isolated upper oil phase solution after being specially and using successively absolute ethyl alcohol and deionized water rinsing, and centrifugation 15min under 11000rmp is with absolute ethyl alcohol wash products twice, again centrifugation 15min under 11000rmp.
Baking temperature in the described step (2) is 65-70 ℃, drying time 2-4h.
The average grain diameter of the cubic crystal type nano silver in the described step (2) is 8.5-9.5nm.
Beneficial effect
(1) the present invention is simple to operate, reaction condition is gentle, and experimental raw is cheap, good economy performance;
(2) the cubic crystal type nano silver granular size that obtains is 8.5-9.5nm, is uniformly dispersed, stablizes, and has a good application prospect.
Description of drawings
Fig. 1 is the process chart of embodiment 1;
Fig. 2 is the transmission electron microscope picture of embodiment 1 products therefrom;
Fig. 3 is the transmission electron microscope picture of embodiment 2 products therefroms;
Fig. 4 is the particle diameter distribution map of embodiment 2 products therefroms;
Fig. 5 is the transmission electron microscope picture of embodiment 3 products therefroms;
Fig. 6 is the particle diameter distribution map of embodiment 3 products therefroms;
Fig. 7 is the transmission electron microscope picture of comparative example's products therefrom.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
1, take by weighing 0.99g(0.00253mol) silver stearate, under 80 ℃, be dissolved in fully in the 85ml cyclohexane, add 0.1423g(2.25 * 10
-4Mol) zinc stearate, magnetic agitation is transparent to solution, saves backup;
2, take by weighing 0.3g(0.00792mol) sodium borohydride, be dissolved at normal temperatures in the 80ml deionized water, magnetic agitation is even, saves backup;
3, join in the silver stearate cyclohexane solution of step 1 preparation in the sodium borohydride 30min with step 2 preparation, at 80 ℃ of lower upper oil phase electric stirrings, the volume ratio of lower floor's water magnetic agitation 2h(oil phase and water is 1:1), add the 100ml absolute ethyl alcohol, the Nano Silver of generation is dispersed in the upper oil phase, then remove lower floor's water, use again the 100ml deionized water rinsing, isolate upper oil phase solution.Take out the 1ml oil phase, ultrasonic with the dilution of 25ml cyclohexane, do the TEM test.Residue oil phase centrifugation 15min under 11000rmp, with absolute ethyl alcohol cleaning deposit twice, centrifugation 15min under 11000rmp again, at last with deposit in vacuum drying chamber, 65 ℃ of lower dry 2h finally obtain the very high nano silver material of purity.TEM figure shows, the product average grain diameter is about 9.4nm, disperses more evenly, and almost do not have agglomeration.
1, take by weighing 0.99g(0.00253mol) silver stearate, under 80 ℃, be dissolved in fully in the 85ml cyclohexane, add 0.5g(2.69 * 10
-3Mol) lauryl amine, magnetic agitation is transparent to solution, saves backup;
2, take by weighing 0.3g(0.00792mol) sodium borohydride, be dissolved at normal temperatures in the 80ml deionized water, magnetic agitation is even, saves backup;
3, join in the silver stearate cyclohexane solution of step 1 preparation in the sodium borohydride 30min with step 2 preparation, at 80 ℃ of lower upper oil phase electric stirrings, the volume ratio of lower floor's water magnetic agitation 3h(oil phase and water is 1:1), add the 100ml absolute ethyl alcohol, the Nano Silver of generation is dispersed in the upper oil phase, then remove lower floor's water, use again the 100ml deionized water rinsing, isolate upper oil phase solution.Take out the 1ml oil phase, ultrasonic with the dilution of 25ml cyclohexane, do the TEM test.Residue oil phase centrifugation 15min under 11000rmp, with absolute ethyl alcohol cleaning deposit twice, centrifugation 15min under 11000rmp again, at last with deposit in vacuum drying chamber, 70 ℃ of lower dry 4h finally obtain the very high nano silver material of purity.TEM figure shows, the product average grain diameter is about 8.65nm, disperses more evenly, and almost do not have agglomeration.
Embodiment 3
1, take by weighing 0.99g(0.00253mol) silver stearate, under 80 ℃, be dissolved in fully in the 85ml cyclohexane, add 0.1g(4.14 * 10
-4Mol) cetylamine, magnetic agitation is transparent to solution, saves backup;
2, take by weighing 0.3g(0.00792mol) sodium borohydride, be dissolved at normal temperatures in the 80ml deionized water, magnetic agitation is even, saves backup;
3, join in the silver stearate cyclohexane solution of step 1 preparation in the sodium borohydride 30min with step 2 preparation, at 80 ℃ of lower upper oil phase electric stirrings, the volume ratio of lower floor's water magnetic agitation 3h(oil phase and water is 1:1), add the 100ml absolute ethyl alcohol, the Nano Silver of generation is dispersed in the upper oil phase, then remove lower floor's water, use again the 100ml deionized water rinsing, isolate upper oil phase solution.Take out the 1ml oil phase, ultrasonic with the dilution of 25ml cyclohexane, do the TEM test.Residue oil phase centrifugation 15min under 11000rmp, with absolute ethyl alcohol cleaning deposit twice, centrifugation 15min under 11000rmp again, at last with deposit in vacuum drying chamber, 70 ℃ of lower dry 4h finally obtain the very high nano silver material of purity.TEM figure shows, the product average grain diameter is about 9.16nm, disperses more evenly, and almost do not have agglomeration.
The comparative example
1, take by weighing 0.99g(0.00253mol) silver stearate, 0.1g(4.14 * 10
-4Mol) cetylamine adds the 85ml cyclohexane, is heated to 60 ℃, and magnetic agitation saves backup;
2, take by weighing 0.3g(0.00792mol) sodium borohydride, be dissolved at normal temperatures in the 80ml deionized water, magnetic agitation is even, saves backup;
3, join in the silver stearate cyclohexane solution of step 1 preparation in the sodium borohydride 30min with step 2 preparation, at 60 ℃ of lower upper oil phase electric stirrings, the volume ratio of lower floor's water magnetic agitation 3h(oil phase and water is 1:1), add the 100ml absolute ethyl alcohol, the Nano Silver of generation is dispersed in the upper oil phase, then remove lower floor's water, use again the 100ml deionized water rinsing, isolate upper oil phase solution.Take out the 1ml oil phase, ultrasonic with the dilution of 25ml cyclohexane, do the TEM test.Residue oil phase centrifugation 15min under 11000rmp, with absolute ethyl alcohol cleaning deposit twice, centrifugation 15min under 11000rmp again, at last with deposit in vacuum drying chamber, 70 ℃ of lower dry 4h finally obtain the very high nano silver material of purity.TEM figure shows, product has agglomeration the granular size heterogeneity to occur.
Claims (10)
1. the method for the protectant preparing cubic crystal nano silver material by oil-water interface of oil-soluble comprises:
(1) silver stearate is dissolved in the cyclohexane under 80 ℃, adds surfactant, be stirred to the solution clear and get silver-colored presoma; Sodium borohydride is dissolved in the deionized water at normal temperatures, and boron hydrogen root presoma stirs to get;
(2) above-mentioned sodium borohydride presoma is joined in the above-mentioned silver-colored presoma, in 80 ℃ of lower upper oil phase electric stirrings, lower floor's water magnetic agitation, the product that obtains is carried out separating, washing, at last product is drying to obtain the cubic crystal type nano ag material.
2. the method for the protectant preparing cubic crystal nano silver material by oil-water interface of a kind of oil-soluble according to claim 1, it is characterized in that: the surfactant in the described step (1) is zinc stearate, cetylamine and lauryl amine.
3. the method for the protectant preparing cubic crystal nano silver material by oil-water interface of a kind of oil-soluble according to claim 1 is characterized in that: in the described step (1) in the cyclohexane concentration of silver stearate be 0.025-0.0375M.
4. the method for the protectant preparing cubic crystal nano silver material by oil-water interface of a kind of oil-soluble according to claim 1 is characterized in that: the concentration 0.075-0.1M of sodium borohydride aqueous solution in the described step (1).
5. the method for the protectant preparing cubic crystal nano silver material by oil-water interface of a kind of oil-soluble according to claim 1, it is characterized in that: the oil phase that contains silver stearate and oleic acid in the described step (2) and the water volume ratio of sodium borohydride are 1:1.
6. the method for the protectant preparing cubic crystal nano silver material by oil-water interface of a kind of oil-soluble according to claim 1 is characterized in that: the speed that the sodium borohydride in the described step (2) adds in the cyclohexane solution is 160min/h.
7. the method for the protectant preparing cubic crystal nano silver material by oil-water interface of a kind of oil-soluble according to claim 1, it is characterized in that: the mixing time in the described step (2) is 2-3h.
8. the method for the protectant preparing cubic crystal nano silver material by oil-water interface of a kind of oil-soluble according to claim 1; it is characterized in that: after the separating, washing in the described step (2) is specially and uses successively absolute ethyl alcohol and deionized water rinsing; isolate upper oil phase solution; centrifugation 15min under 11000rmp; with absolute ethyl alcohol wash products twice, centrifugation 15min under 11000rmp again.
9. the method for the protectant preparing cubic crystal nano silver material by oil-water interface of a kind of oil-soluble according to claim 1, it is characterized in that: the baking temperature in the described step (2) is 65-70 ℃, drying time 2-4h.
10. the method for the protectant preparing cubic crystal nano silver material by oil-water interface of a kind of oil-soluble according to claim 1, it is characterized in that: the average grain diameter of the cubic crystal type nano silver in the described step (2) is 8.5-9.5nm.
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Cited By (1)
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| CN107775013A (en) * | 2017-10-26 | 2018-03-09 | 中国科学技术大学 | Ag is nanocrystalline, its preparation method and its application |
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| US20110203414A1 (en) * | 2010-02-25 | 2011-08-25 | National Tsing Hua University | Methods for preparing hydrophobic metal nanoparticles and precursors used therein |
| CN102179526A (en) * | 2011-04-18 | 2011-09-14 | 东华大学 | Method for preparing cubic crystal nano silver material by oil-water interface method |
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| US7002044B2 (en) * | 2002-08-15 | 2006-02-21 | The University Of Connecticut | Catalysis by water-soluble organometallic complexes in water-in-densified fluid microemulsions |
| CN1416988A (en) * | 2002-11-30 | 2003-05-14 | 中国科学院兰州化学物理研究所 | Oil soluble metal silver nano-powder and its prepn process |
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| CN107775013A (en) * | 2017-10-26 | 2018-03-09 | 中国科学技术大学 | Ag is nanocrystalline, its preparation method and its application |
| CN107775013B (en) * | 2017-10-26 | 2020-01-03 | 中国科学技术大学 | Ag nanocrystal, preparation method and application thereof |
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