A kind of preparation method of different-shape nano silver sol
Technical field:
The invention belongs to the nano material preparing technical field, be specifically related to a kind of preparation method of different-shape nano silver sol.
Background technology:
Silver ion antimicrobial agent occupies leading position in inorganic antiseptic, on market, most commercial inorganic antibacterial bactericide are all to carry silver.Nano silver colloidal sol is widely used as the antiseptic of health care, coating, fibre, sports goods, plastic products etc., and the technology of preparing of the extensive use of nano silver colloidal sol and nano silver colloidal sol maturation is closely-related.
Chemical reduction method is to prepare at present nano silver colloidal sol preparation method the most widely, this method mainly utilizes one or several in glucose, ascorbic acid, boron hydride, sodium metaphosphate, sodium hypophosphite, trisodium citrate, hydrogen peroxide, hydrazine hydrate, ethylene glycol, polyethylene glycol or glycerine as reducing agent, is the nanometer elargol with silver nitrate reduction.This method production equipment is simple, technological process is simple and easy to control, especially for the preparation of nanometer elargol, can realize at present spherical, cube, the synthetic (Y.G.Sun of control of the different-shapes such as hexagon, pentagon, triangle, Y.N.Xia.Science, 2002,298 (13): 2176-2179; Y.N.Xia, Y.J.Xiong, B.Lim, S.E.Skrabalak.Angew.Chem.Int.Ed., 2008,47,2-46; A.R.Siekkinen, J.M.McLellan, J.Chen, Y.N.Xia.Chem.Phys.Lett., 2006,432,491-496.).But the nano silver colloidal sol existence and stability of most methods preparation is poor, reaction is difficult to control and can't mass industrialized production etc. shortcoming.
Chinese patent CN1557588A discloses a kind of manufacture method of Nano Silver: main source take silver nitrate as silver particles, take isopropyl alcohol as the aqueous solution in the free scavenger of oxidisability; And the speed of growth of controlling nucleus by hydrophilic surface active agent polyvinyl alcohol is to control particle size, the electron beam that utilizes electron accelerator to produce carries out radiation treatment, with the solution after irradiation through wash, centrifugation, oven dry is although get final product to get the method Nano Silver powder of black.Thisly can obtain Nano Silver, but adopt electron beam irradiation, need the expensive equipment of cover, increase production cost.
Summary of the invention:
In order to overcome the deficiency of existing technology, the object of the present invention is to provide a kind of with low cost, easy, preparation method mass production different-shape nano silver sol under water solution system and normal temperature and pressure simple to operate.
2AgNO
3+Na
2S
2O
4+4NaOH=2Ag+2Na
2SO
3+2NaNO
3+2H
2O
According to above-mentioned reaction, the present invention adopts sodium dithionite (sodium hydrosulfite) to prepare the reducing agent of nanometer elargol for liquid-phase reduction, adopting different surfactants is dispersant, and the reduction silver nitrate obtains making the fulmargin of different-shape, stably dispersing under alkali condition.
The invention provides a kind of preparation method of different-shape nano elargol, it is characterized in that: described method is carried out successively as follows:
(1) silver nitrate that takes certain mass is dissolved in deionized water, makes certain density liquor argenti nitratis ophthalmicus, and the water soluble surfactant active is dissolved in mentioned solution, mixes, and wherein, the mass ratio of silver nitrate and surfactant is 1: 0.5-1: 12.
(2) produce the solution that finite concentration contains the dithionite reducing agent, high-concentration sodium hydroxide solution is added in mentioned solution, adjust pH=11, mix.
(3) reductant solution with step (2) adds in the liquor argenti nitratis ophthalmicus that contains surfactant, dripping speed is the 0.5-20 ml/min, use simultaneously magnetic stirrer, drip rear continuation stirring reaction 0.5-1h, namely make nano silver colloidal sol, wherein the reducing agent molal weight be silver nitrate 1-3 doubly.
Preferably, the concentration of described liquor argenti nitratis ophthalmicus is 0.005mol/L-0.05mol/L.
Preferably, the concentration of described reductant solution is 0.005mol/L-0.05mol/L.
Described reducing agent is sodium dithionite (sodium hydrosulfite).
Described surfactant is selected from one or more in laruyl alcohol PEO ether sulfuric acid, polyvinylpyrrolidone, alkyl phosphate diethanolamine salt antistatic additive P, imidazoline, ester quat type cationic surfactant 1227, AEO silane WA, softex kw, antistatic additive PK.
The color of the nanometer elargol that the present invention is prepared can be bronzing, dark brown, light yellow, yellow, buff, pink, dirty-green, blueness etc.
Preparation method's beneficial effect provided by the present invention is: not only have reaction condition gentleness (normal temperature and pressure), the characteristics such as with low cost, easy and simple to handle, with short production cycle, and prepared nano silver colloidal sol diameter of particle in the 10-90nm scope and dispersion stabilization good, can stablize and preserve more than 1 year.
Description of drawings:
Fig. 1 is the process chart of the embodiment of the present invention, and wherein, 1 fully mixes for silver nitrate and surfactant; 2 regulate pH for sodium hydroxide solution adds in reductant solution; 3 fully react for reductant solution is added drop-wise in liquor argenti nitratis ophthalmicus; 4 is the target product Performance Detection.
Fig. 2 is the XRD picture of the nanometer elargol that makes of embodiment 1.
Fig. 3 is the transmission electron microscope photo of the nanometer elargol that makes of embodiment 1.
Fig. 4 is the transmission electron microscope photo of the nanometer elargol that makes of embodiment 2.
Fig. 5 is the transmission electron microscope photo of the nanometer elargol that makes of embodiment 3.
Fig. 6 is the transmission electron microscope photo of the nanometer elargol that makes of embodiment 4.
The specific embodiment:
The present invention will be further described below in conjunction with accompanying drawing 1 and embodiment.
Embodiment 1
Take the 0.34g silver nitrate and be mixed with deionized water the liquor argenti nitratis ophthalmicus that 400ml concentration is 0.05mol/L, then take 0.68g surfactant laruyl alcohol PEO ether sulfuric ester and be dissolved in (mass ratio of laruyl alcohol PEO ether sulfuric ester and silver nitrate is 2: 1) in above-mentioned silver nitrate aqueous solution, stir; Take the 0.522g sodium dithionite and be mixed with the hydrosulfurous acid sodium solution that 600ml concentration is 0.05mol/L (mol ratio of silver nitrate and sodium hydrosulfite is 1: 1.5) with deionized water, add high concentration NaOH solution to adjust pH=11; Then the hydrosulfurous acid sodium solution is added drop-wise in liquor argenti nitratis ophthalmicus with the speed of 20 ml/min at normal temperatures and pressures, uses simultaneously magnetic stirrer, stir 30min wait dripping rear continuation, finally can get jonquilleous nano silver colloidal sol.
Prepared sample is carried out the properties test, and test case and result thereof are as follows:
With X-ray diffraction analysis (XRD), can determine that by accompanying drawing 2 prepared colloidal sol is nano silver colloidal sol; Utilize transmission electron microscope to observe, by accompanying drawing 3 as can be known, micelle is the spherical nano-silver of average grain diameter 10nm left and right.
Embodiment 2
Take the 0.17g silver nitrate and be mixed with deionized water the liquor argenti nitratis ophthalmicus that 500ml concentration is 0.002mol/L, then take 1.7g surfactant imidazoles woods and be dissolved in (mass ratio of imidazoles woods and silver nitrate is 10: 1) in above-mentioned silver nitrate aqueous solution, stir; Take the 0.522g sodium dithionite and be mixed with the hydrosulfurous acid sodium solution that 600ml concentration is 0.005mol/L (mol ratio of silver nitrate and sodium hydrosulfite is 1: 3) with deionized water, add high concentration NaOH solution to adjust pH=11; Then the hydrosulfurous acid sodium solution is added drop-wise in liquor argenti nitratis ophthalmicus with the speed of 15 ml/min at normal temperatures and pressures, uses simultaneously magnetic stirrer, stir 30min wait dripping rear continuation, finally can get nano silver colloidal sol russet.By accompanying drawing 4 as can be known, micelle is the spherical nano-silver of average grain diameter 16nm left and right.
Embodiment 3
Take the 0.26g silver nitrate and be mixed with deionized water the liquor argenti nitratis ophthalmicus that 500ml concentration is 0.003mol/L, then take 0.78g quaternary ammonium salt cationic surfactant 1227 and be dissolved in (quaternary ammonium salt cationic surfactant 1227 is 3: 1 with the mass ratio of silver nitrate) in above-mentioned silver nitrate aqueous solution, stir; Take the 0.522g sodium dithionite and be mixed with the hydrosulfurous acid sodium solution that 500ml concentration is 0.06mol/L (mol ratio of silver nitrate and sodium hydrosulfite is 1: 2) with deionized water, add high concentration NaOH solution to adjust pH=11; Then the hydrosulfurous acid sodium solution is added drop-wise in liquor argenti nitratis ophthalmicus with the speed of 0.5 ml/min at normal temperatures and pressures, uses simultaneously magnetic stirrer, stir 30min wait dripping rear continuation, finally can get pink nano silver colloidal sol.By accompanying drawing 5 as can be known, micelle is the irregular hexagon Nano Silver in average grain diameter 45nm left and right.
Embodiment 4
Take the 0.51g silver nitrate and be mixed with deionized water the liquor argenti nitratis ophthalmicus that 100ml concentration is 0.03mol/L, then take 0.26g polyvinylpyrrolidone surfactant and be dissolved in (mass ratio of polyvinylpyrrolidone and silver nitrate is 0.5: 1) in above-mentioned silver nitrate aqueous solution, stir; Take the 1.04g sodium dithionite and be mixed with the hydrosulfurous acid sodium solution that 100ml concentration is 0.06mol/L (mol ratio of silver nitrate and sodium hydrosulfite is 1: 2) with deionized water, add high concentration NaOH solution to adjust pH=11; Then the hydrosulfurous acid sodium solution is added drop-wise in liquor argenti nitratis ophthalmicus with the speed of 1 ml/min at normal temperatures and pressures, uses simultaneously magnetic stirrer, stir 1h wait dripping rear continuation, finally can get blue nano silver colloidal sol.By accompanying drawing 6 as can be known, micelle is the discoid Nano Silver of average grain diameter 90nm left and right.