A kind of preparation method who contains the water-soluble nano silver powder of living beings
Technical field
The present invention relates to a kind of preparation method of water-soluble nano silver powder.
Background technology
Nano material receives much attention owing to its quantum size effect, small-size effect, surface interface effect and macro quanta tunnel effect demonstrate good optics, calorifics, magnetics, mechanics, electricity and chemical property.Nano Silver is widely used in fields such as catalysis, antibiotic, electronic circuits, at SERS (SERS), novel hydrogen storage material, composite electrode, low temperature Heat Conduction Material etc. suitable application prospect is arranged also.
Physical methods such as chemical method such as liquid phase chemical reduction, photoreduction, microemulsion and high-energy ball milling, laser splash, laser ablation are mainly adopted in the preparation of Nano Silver at present both at home and abroad.Photoreduction method reaction speed is slower, especially for the preparation production of fairly large product.Microemulsion method complex process, operation are harsh relatively.Physical methods such as high-energy ball milling, laser splash, laser ablation require high to equipment, and energy consumption is higher, is unfavorable for suitability for industrialized production.The liquid phase chemical reduction method is because its technology is simple relatively, and operation is relatively easy, and production cost is lower, is the method for the most normal employing.It utilize suitable reducing agent such as zinc powder, hydrazine hydrate, natrium citricum etc. in liquid phase with the silver salt reaction, be silver-colored simple substance particle with silver ion reduction.Must add some organic polymers as dispersant, protective agent, as polyvinylpyrrolidone (PVP), aniline, double hexadecyl phosphordithiic acid pyridiniujm (PyDDP) etc. in order to prevent that Nano Silver from reuniting in the process.At present, still there are some problems in the liquid phase chemical reduction method, comprising: can not control well course of reaction and process conditions; A certain ad hoc approach can only be prepared the nano-silver powder of a certain specific average grain diameter; Can't from nano silver colloidal sol, isolate the single dispersed nano silver powder of solid preferably; The difference of dispersive property once more of final products nano-silver powder etc.
In recent years, biological absorption is because it becomes the focus of research in the application prospect aspect the environmental protection, the researcher find with the biological adsorption agent processing as Ag
+Wait some metal ion to be accompanied by the redox phenomenon often, the metal simple-substance particle is arranged at the biological adsorption agent surface deposition.D01 can be with Ag as bacillus megaterium (Bacillus megaterium)
+Be reduced into Ag
0, obtain nano level silver-colored particle [SCI, 1999,20 (9): 1452] at cell surface; The Ag of Bacillus acidi lactici (Lactobacillussp.) A09 dry bacterium powder in also can reducing solution
+, accumulate the silver-colored polycrystalline particulate [Acta PhySico-Chimica Sinica, 2000,16 (9): 779] of cataphracted black not of uniform size, skewness on the thalline surface; Utilize corynebacteria (Corynebacterium) SH09 can under 60 ℃ of conditions, prepare the silver sol [Journal of Chemical Technology andBiotechnology, 2005,80 (3): 285] of 10~15 nm; Utilize verticillium sp (Verticillium) at 28 ℃ of silver sols [Nano Letters, 2001,1:515] that can prepare 25 ± 12nm down; Utilize sickle mycete (Fusarium oxysporum) can prepare the silver sol [Colloids and Surfaces B-Biointerface, 2003,28:313] of 5~15nm at ambient temperature; Utilize aspergillus fumigatus (Aspergillus fumigatus) can under 25 ℃ of conditions, prepare the silver sol [Colloids and Surfaces B:Biointerfaces, 2006,47:152] of 5~25nm.Fu Jinkun etc. once isolated bacillus licheniformis (Bacillus licheniformis) R08[ZL02102604.1 from goldfield soil and pit water] and bacillus megaterium (Bacillus megaterium) D01[ZL00101516.8], and adopt these bacterial strains to adsorb effectively and reduce palladium ion and gold ion.
Summary of the invention
Purpose of the present invention aims to provide a kind of method of utilizing microbial cell to prepare water-soluble nano silver powder as reducing agent and protective agent; prepared water-soluble nano silver powder average grain diameter can have good dispersiveness and stability in the aqueous solution in 5~15nm scope.
The preparation method of the water-soluble nano silver powder that contains living beings of the present invention is as follows:
1. will enlarge the bacillus licheniformis R08 or the bacillus megaterium D01 bacterium mud drying of cultivating, grind that to make the bacterium powder standby;
2. the bacterium powder that will contain microorganism is mixed with the bacteria suspension of 0.1~200g/L, mix with NaOH solution, silver compound again, 30~90 ℃ of following water-bath heating, vibration, reaction 2~30h, obtain containing the mixed liquor of microbial body and nano silver colloid, described silver compound can be silver ammino solution, liquor argenti nitratis ophthalmicus or silver oxide solid; The microbial dry powder mass concentration is 0.3~5 with the ratio of the mass concentration of silver in the reaction system, and is preferred 0.5~2, and the ratio of NaOH molar concentration and the molar concentration of silver is 1~40, preferred 2~20;
3. with the mixed liquor centrifugation of microbial body and nano silver colloid, discard the microbial body relic, obtain the silver sol that contain living beings of stable buff to black;
4. evaporation and concentration living beings silver sol, the stirring vibration adds organic solvent down precipitates the dehydration of elargol grain, filter or centrifugation collecting precipitation and 30~60 ℃ of following vacuum drying, obtain containing the water-soluble nano silver powder of living beings, described organic solvent is ethanol or acetone.
The present invention has utilized under alkali condition, and the organo-functional group that enriches on the microbial cell comprises some reproducibility groups such as aldehyde radical, and the silver ion that oxidisability is stronger (or complex ion) is reduced to argent simple substance.Since groups such as the polyhydroxy on the living beings, carboxyl can and silver metal simple substance between produce stronger interaction force, living beings have played the effect of the silver-colored particle of parcel protection, and silver-colored simple substance particle also is limited in nanoscale.The percentage composition of silver is 60~80% (W%) in the prepared water-soluble nano silver powder; The silver particle is spherical in shape, and particle diameter is evenly distributed, and average grain diameter can have good dispersiveness and stability in the aqueous solution in 5~15nm scope.This nano-silver powder is being expected to have a good application prospect aspect antibiotic and the Preparation of Catalyst.
Description of drawings
Fig. 1 is the XRD figure spectrum of the nano-silver powder of the embodiment of the invention 1 preparation.In Fig. 1, abscissa is angle 2 θ, and the characteristic peak of silver-colored elemental crystal is followed successively by (111), d=2.3528 from left to right; (200), d=2.0531; (220), d=1.4426; (311), d=1.2311; (222), d=1.1794, wherein d is the diameter of silver-colored elemental crystal.
Fig. 2 is the HRTEM figure of the nano-silver powder of the embodiment of the invention 1 preparation.In Fig. 2, scale is 20nm.
The specific embodiment
The invention will be further described below by embodiment.
Embodiment 1:
Contain the preparation of microbial cell bacteria suspension: take by weighing the R08 dry bacterium powder of 1.0g porphyrize, add the 80mL deionized water, the stirring vibration is evenly standby; The preparation of silver ammino solution: take by weighing the 15.74g silver nitrate, add the appropriate amount of deionized water dissolving, the ammonia spirit of dropping 10% just disappears up to precipitation, is settled to 100mL with deionized water; The NaOH solution of preparation 2mol/L.
In the 500mL conical flask bacteria suspension 80mL, silver ammino solution 10mL, NaOH solution 10mL are mixed, then bacterium powder concentration is 10g/L in the reaction system, and silver concentration is 10g/L, and the NaOH solution concentration is 0.2mol/L.Place 60 ℃ of shaking baths (120rpm/min) oscillating reactions 8h to make the mixed liquor of mycetome relic, nano silver colloidal sol mixed liquor; To react back mixed liquor centrifugation (3000rpm/min), and discard the thalline relic and obtain the stable silver sol that contains certain living beings.
With silver sol in 60 ℃ of baking ovens evaporation and concentration to about 10mL; Stir fast and add absolute ethyl alcohol 30mL down, the elargol grain precipitation of dewatering rapidly; Obtain elargol grain sediment with qualitative filter paper isolated by filtration at a slow speed, once more with twice of absolute ethanol washing precipitation; Collecting precipitation obtains containing the water-soluble nano silver powder of living beings in 60 ℃ of following vacuum drying 2h.The mass fraction of silver is about 71% in the silver powder.The XRD figure spectrum of nano-silver powder is as Fig. 1.Observation post gets silver powder (as shown in Figure 2) under high power transmission electron microscope (HRTEM), and silver-colored particle is spherical in shape, the single dispersion.By SigmaScan Pro software several silver-colored particle photos are handled, obtained each particle grain size in the picture, carry out the particle diameter distribution statistics with Origin 7.5 softwares, statistics shows the about 6.2nm of the average grain diameter of silver-colored particle.
Embodiment 2:
Adopt the preparation of D01 dry bacterium powder to contain the bacteria suspension of microbial cell, in the 500mL conical flask, mix each component, the concentration of mixing bacteria suspension, silver nitrate and NaOH in the afterreaction system is respectively 10g/L, 10g/L and 0.2mol/L, place 60 ℃ of shaking baths (120rpm/min) oscillating reactions 10h, all the other are with embodiment 1.Get silver powder with HRTEM observation post, silver-colored particle is spherical in shape, the single dispersion, and the about 10.1nm of elargol grain average grain diameter, the mass fraction of silver is about 63% in the silver powder.
Embodiment 3~6
Adopt the R08 dry bacterium powder among the embodiment 1, the concentration of silver ammino solution and NaOH solution is fixed as 1g/L and 0.2mol/L respectively in the reaction system, changes the concentration of R08 bacteria suspension, repeats the preparation procedure identical with embodiment 1.The average grain diameter of prepared nano-silver powder sees Table 1 under the different bacterium powder concentration.
Table 1
Embodiment |
Bacterium powder concentration (g/L) |
Reaction time (h) |
Average grain diameter (nm) |
3 |
0.5 |
4 |
11.6 |
4 |
1 |
6 |
8.2 |
5 |
2 |
12 |
6.6 |
6 |
5 |
30 |
5.8 |
Embodiment 7~12
Adopt the R08 dry bacterium powder among the embodiment 1, the concentration of R08 bacteria suspension and silver ammino solution concentration all are fixed as 1g/L in the reaction system, change the NaOH solution concentration, repeat the preparation procedure identical with embodiment 1.The average grain diameter of prepared nano-silver powder sees Table 2 under the different N aOH concentration.
Table 2
Embodiment |
NaOH concentration (mol/L) |
Reaction time (h) |
Average grain diameter (nm) |
7 |
0.01 |
16 |
5.2 |
8 |
0.02 |
8 |
5.9 |
9 |
0.05 |
6 |
6.3 |
10 |
0.1 |
4 |
6.8 |
11 |
0.2 |
2 |
7.6 |
12 |
0.4 |
2 |
10.3 |
Embodiment 13:
Adopt the R08 dry bacterium powder among the embodiment 1, in the 500mL conical flask, mix each component, the concentration of mixing bacteria suspension, silver nitrate and NaOH in the afterreaction system is respectively 1g/L, 1g/L and 0.05mol/L, place 60 ℃ of shaking baths (120rpm/min) oscillating reactions 12h, all the other preparation methods are with embodiment 1.Get silver powder with HRTEM observation post, silver-colored particle is spherical in shape, the single dispersion, and the about 7.1nm of elargol grain average grain diameter, the mass fraction of silver is about 70% in the silver powder.
Embodiment 14:
Adopt the R08 dry bacterium powder among the embodiment 1, in the 500mL conical flask with 0.107g Ag
2O powder and bacteria suspension and NaOH solution mix, bacteria suspension and NaOH concentration are respectively 1g/L and 0.05mol/L in the mixing afterreaction system, place 60 ℃ of shaking baths (120rpm/min) oscillating reactions 20h, adopt acetone to make elargol grain dehydration precipitation, the centrifugation collecting precipitation, all the other preparation methods are with embodiment 1.With tem observation gained silver powder, silver-colored particle is spherical in shape, and particle diameter is even, and average grain diameter is less than 10nm.The mass fraction about 76% of silver in the silver powder.