CN102554258A - Method for preparing metal silver nanostructure in water solution - Google Patents
Method for preparing metal silver nanostructure in water solution Download PDFInfo
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- CN102554258A CN102554258A CN2012100240059A CN201210024005A CN102554258A CN 102554258 A CN102554258 A CN 102554258A CN 2012100240059 A CN2012100240059 A CN 2012100240059A CN 201210024005 A CN201210024005 A CN 201210024005A CN 102554258 A CN102554258 A CN 102554258A
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Abstract
The invention discloses a method for preparing a metal silver nanostructure in water solution, which includes the steps: determining types and proportions of initial reactants according to requirements of different morphologies and evenly mixing the initial reactants to obtain precursor water solution; growing silver nanostructures in the precursor water solution at the constant temperature of 50-105 DEG C; and centrifugally separating and washing reaction solution to obtain silver nanostructures of different morphologies. Inert gas for protection is omitted, reaction temperature is low, the preparation process is simple, the cost is low, and the method overcomes the shortcomings of complicated preparation procedures, low yield, high cost and the like of a traditional polyhydroxy reduction method, a traditional illumination method and a traditional oxidation reduction method, and has important significance for industrial mass production and practical application of the silver nanostructures of different morphologies.
Description
Technical field
The present invention relates to a kind of method that in the aqueous solution, prepares the argent nanostructured, belong to the Nano Silver preparing technical field.
Background technology
Different-shape silver nanostructured is because its potential application at nanoelectronics, magnetics, biology sensor, storage, catalysis, SERS and aspect such as antibiotic has become a very active research field.The focus of nano materials research turns to the exploitation of nano functional device gradually from the preparation of nano material, the diversification microminiaturized day by day and complicated pattern to nano material of nano-device is had higher requirement.The performance of metal nano material depends on pattern, size, composition, degree of crystallinity and the structure of particle to a great extent.Therefore, the silver nanostructured preparation of pattern and controllable size seems very important.For example, little, the narrow particle size distribution of the particle diameter of spherical silver nano particle is the material with satisfactory electrical conductivity, can be used as good electrode material.Therefore, the spherical silver nano material of preparation rule, very crucial to the performance that improves battery.But at present less about the report of the controlled silver-colored nanosphere of preparation size, the silver-colored nanosphere of therefore synthetic controllable size has certain meaning.Contact between sheet is silver nanostructured is face contact or line contact, so resistance is relatively low, electric conductivity is better, and they are shown and the distinct optical property of spheroidal particle.And the silver nanostructured specific area of sheet is bigger; The surface can be lower, non-oxidizability is strong; Nanostructured than other pattern is stable, strengthens fields such as fluorescence spectrum, infrared thermotherapy, biomarker, nano conductive adhesive electronic package material at catalysis, SERS, metal and has great using value.At present; The silver nanostructured preparation method of sheet mainly contains photo-induction inducing defecation by enema and suppository, thermal transition method, template and solwution method etc.; Wherein photo-induction inducing defecation by enema and suppository, thermal transition method and template operation more complicated, productive rate is lower, and aqua-solution method output is high, cost is low; Operating easylier, is the common method of at present low-cost preparation Nano silver piece.For example, (Langmuir 2010,26 (14), and 11621-11623) group adopts the stable oxide-reduction method of natrium citricum to synthesize Nano silver piece, but the pattern of end product is irregular, and the adjustable range of size narrow (42-22.9 nm) for Roh.Stamplecoskie (J. AM. CHEM. SOC. 2010,132, it is silver nanostructured that 1825-1827) the stable photochemical method of group employing natrium citricum has synthesized sheet, but the pattern of end product is irregular, and size is uncontrollable.The silver nanostructured polyhydroxy reducing process that adopt of cube bulk and wire more, the aqueous solution is synthetic to such silver nanostructured synthetic advantages of simplicity and high efficiency approach that provides, and it is low to have a cost; Environmental protection; Advantage such as economize on resources, and preparation process favorable repeatability, control easily.
Summary of the invention
Irregular, the shortcomings such as size is single, complicated operation of Nano Silver pattern to existing in the prior art; The invention provides a kind of method that in the aqueous solution, prepares the argent nanostructured; This method can prepare the argent nanostructured of pattern, size adjustable; Simple to operate, do not need inert gas shielding, low, the good reproducibility of reaction temperature.
The present invention utilizes the silver nanostructured of the synthetic different-shape of sodium borohydride reduction method one step preparation, is reflected in the aqueous solution and carries out, and process is simple, good reproducibility, and concrete technical scheme is following:
A kind of method that in the aqueous solution, prepares the argent nanostructured may further comprise the steps:
(1) preparation of the predecessor aqueous solution: with silver nitrate aqueous solution and reproducibility compound, add alkali halide and pyrrolidones stabilizing agent then, add sodium borohydride after stirring again, stir and obtain the uniform precursor aqueous solution;
(2) silver nanostructured growth: adopt in following a or the b method any to continue to handle predecessor aqueous solution, preparation different-shape silver nanostructured:
A. with the predecessor aqueous solution of step (1) at 50～105 ℃ of following isothermal reaction 3～100 h;
B. get the described predecessor aqueous solution of step (1), keep its temperature, slowly inject silver nitrate aqueous solution then, inject continued reaction 5～50 h that finish at 50～105 ℃;
(3) after step (2) reaction finishes,, obtain the silver nanostructured of different-shape with reactant liquor centrifugation, washing.
Among the above-mentioned preparation method, said reproducibility compound is natrium citricum, ascorbic acid or cetyltrimethylammonium base amine; Said pyrrolidones stabilizing agent is polyvinylpyrrolidone, N-methyl pyrrolidone, vinyl pyrrolidone or 2-Pyrrolidone; Said alkali halide is sodium chloride, potassium chloride, sodium bromide, KBr, sodium iodide or KI.
Among the above-mentioned preparation method, in the step (1), silver nitrate: alkali halide: reproducibility compound: pyrrolidones: the mass ratio of sodium borohydride is 0.1～10: 0～6: 0～10: 1～100: 0.001～1.
Among the above-mentioned preparation method; With silver nitrate, reproducibility compound, pyrrolidones, alkali halide, sodium borohydride is reactant; Be made into the predecessor aqueous solution, be reflected in the aqueous solution and carry out, mix in order to make each material; Except that sodium borohydride, silver nitrate, reproducibility compound, pyrrolidones and alkali halide all add with the form of the aqueous solution.The concentration of each reactant in precursor solution has certain influence to the pattern of end product, considers the unicity of end product pattern, the uniformity of size, and in the step (1), the concentration of silver nitrate is preferably 1～5 * 10 in the predecessor aqueous solution
2Mmol/L, the reproducibility compound concentrations is 0～9 * 10
2Mmol/L, the concentration of alkali halide is 0～2 * 10
2Mmol/L, the concentration of pyrrolidones stabilizing agent is 0～7 * 10
4Mmol/L.
Silver nanostructured can the growth through two kinds of forms; A kind of is that the predecessor aqueous solution does not add any reagent; Directly under the temperature and time of setting, react, it is silver nanostructured to grow, and another kind is in the predecessor aqueous solution, to continue to add silver nitrate aqueous solution; And then under the temperature and time of setting, react, it is silver nanostructured to grow.Wherein silver nitrate aqueous solution adds in the predecessor aqueous solution in two ways; A kind of method is: silver nitrate aqueous solution with the injection rate of 1mL/min inject the predecessor aqueous solution; It is that 1:0.01～3 o'clock stop to inject that the silver nitrate that injects reaches mass ratio with predecessor aqueous solution silver nitrate, and the concentration of used silver nitrate aqueous solution is 1～10 * 10
3Mmol/L; Second method is: silver nitrate aqueous solution with the injection rate of 0.01mL/min inject the predecessor aqueous solution; It is that 1:2～16 o'clock stop to inject that the silver nitrate that injects reaches mass ratio with predecessor aqueous solution silver nitrate, and the concentration of used silver nitrate aqueous solution is 1～10 * 10
3Mmol/L.
The silver nanostructured pattern of the present invention mainly confirms that by the amount ratio of initial reactants such as reproducibility compound, stabilizing agent, alkali halide the silver nanostructured pattern of gained is sphere, triangle sheet, cube bulk, nano bar-shape, nanometer wire etc.
When growth is silver nanostructured; Precursor solution all keeps 50-105 ℃; Reaction time is slightly different; The rate of addition of temperature, time, silver nitrate is bigger to gained silver nanostructured size and size impact, silver nanostructured size Control reaction temperature and time that in the preparation can be according to actual needs.In technical scheme scope of the present invention; The diameter of silver nanosphere about 3-100 nm, the silver nanostructured length of side of triangle sheet about 10-150 nm, the silver nanostructured length of side of cube bulk about 50-200 nm, the draw ratio of silver-colored nanometer rods and nano silver wire about 3-100, diameter is about 10-500 nm.
This method is through the influence to silver nanostructured growth kinetics of control reproducibility compound, stabilizing agent, alkali halide; Synthesize and have the argent nanostructured of various patterns; Because these silver nanostructured narrow particle size distributions, granularity is adjustable, and electric conductivity is good; Can be used as good electrode material, have great using value in fields such as catalysis, SERS, biomarker, nano conductive adhesive electronic package materials.
The present invention adopts sodium borohydride one stage reduction method to prepare the Nano Silver structure; Be reflected in the aqueous solution and carry out; Adopt the silver nanostructured patterns of material control such as stabilizing agent; Need not to feed inert gas shielding, reaction temperature is low, and the preparation process is simple, output is high, cost is low; Overcome the preparation procedure that exists in the methods such as crystal seed method, luminescence method, traditional polyhydroxy reducing process complicated, yield poorly, the high deficiency of cost, thereby the present invention will be significant to silver nanostructured mass industrialized production and practical application thereof.
Description of drawings
Fig. 1 is transmission electron microscope photo (TEM) picture of the synthetic silver-colored nanosphere of the embodiment of the invention 1.
Fig. 2 is transmission electron microscope photo (TEM) picture of the synthetic silver-colored nanosphere of the embodiment of the invention 2.
Fig. 3 is transmission electron microscope photo (TEM) picture of the synthetic silver-colored nanosphere of the embodiment of the invention 4.
Fig. 4 is transmission electron microscope photo (TEM) picture of the synthetic Nano silver piece of the embodiment of the invention 5.
Fig. 5 is transmission electron microscope photo (TEM) picture of the synthetic Nano silver piece of the embodiment of the invention 7.
Fig. 6 is transmission electron microscope photo (TEM) picture of the synthetic Nano silver piece of the embodiment of the invention 9.
The specific embodiment
Through embodiment the present invention is further set forth below, should be understood that, following explanation only is in order to explain the present invention, its content not to be limited.
Embodiment 1
1.1 the silver nitrate aqueous solution that is 30 mM to 3 mL concentration mixes with the aqueous solution 10 mL of natrium citricum; The aqueous solution that adds 3 mL sodium chloride and polyvinylpyrrolidone afterwards; After the mixing and stirring; Add 1.5 mg sodium borohydride powder, obtain the uniform aqueous solution after the stirring, wherein the weight ratio of silver nitrate/sodium chloride/sodium citrate/polyvinylpyrrolidone/sodium borohydride is 6: 1: 5: 3: 0.5.
1.2 get the embodiment 1.1 described aqueous solution 10 mL, be placed in 100 ℃ the oil bath isothermal reaction 32 h.
It is after 1.3 reaction finishes,, as shown in Figure 1 through obtaining the silver-colored nanosphere that average diameter is 23 nm after centrifugation and the washing.
Embodiment 2
2.1 the silver nitrate aqueous solution that is 450 mM to 2 mL concentration mixes with the aqueous solution 10 mL of natrium citricum; The aqueous solution that adds 3 mL sodium chloride and polyvinylpyrrolidone afterwards; After the mixing and stirring; Add 1.5 mg sodium borohydride powder, obtain the uniform aqueous solution after the stirring, wherein the weight ratio of silver nitrate/sodium chloride/sodium citrate/polyvinylpyrrolidone/sodium borohydride is 6: 1: 5: 7: 0.5.
2.2 get the embodiment 2.1 described aqueous solution 10 mL, be placed in 90 ℃ the oil bath isothermal reaction 26 h.
It is after 2.3 reaction finishes,, as shown in Figure 2 through obtaining the silver-colored nanosphere that average diameter is 8.5 nm after centrifugation and the washing.
Embodiment 3
3.1 is 0.6 mL concentration that 100 mM silver nitrate aqueous solutions mix with the aqueous solution 12 mL of ascorbic acid; The aqueous solution that adds 2 mL potassium chloride and N-methyl pyrrolidone afterwards; After the mixing and stirring; Add 1.5 mg sodium borohydride powder, obtain the uniform aqueous solution after the stirring, wherein the weight of silver nitrate/potassium chloride/ascorbic acid/N-methyl pyrrolidone/sodium borohydride is 6: 1: 5: 7: 0.5.
3.2 get the embodiment 3.1 described aqueous solution 10 mL, be placed in 80 ℃ the oil bath isothermal reaction 40 h.
After 3.3 reaction finishes, through obtaining the silver-colored nanosphere that average diameter is 80 nm after centrifugation and the washing.
4.1 the silver nitrate aqueous solution that is 90 mM to 1 mL concentration mixes with the aqueous solution 5 mL of natrium citricum; The aqueous solution that adds 5 mL sodium chloride and polyvinylpyrrolidone afterwards; After the mixing and stirring; Add 1.5 mg sodium borohydride powder, obtain the uniform aqueous solution after the stirring, wherein the weight ratio of silver nitrate/sodium chloride/sodium citrate/polyvinylpyrrolidone/sodium borohydride is 2: 0.3: 2: 1: 0.3.
4.2 get the embodiment 4.1 described aqueous solution 10 mL, be placed in 100 ℃ the oil bath isothermal reaction 6 h.
It is after 4.3 reaction finishes,, as shown in Figure 3 through obtaining the silver-colored nanosphere that average diameter is 6 nm after centrifugation and the washing.
Embodiment 5
5.1 the silver nitrate aqueous solution that is 2.3 mM to 6 mL concentration mixes with the aqueous solution 10 mL of natrium citricum; The aqueous solution that adds 4 mL polyvinylpyrrolidones afterwards; After the mixing and stirring; Add 0.23 mg sodium borohydride powder, obtain the uniform aqueous solution after the stirring, wherein the weight ratio of silver nitrate/sodium chloride/sodium citrate/polyvinylpyrrolidone/sodium borohydride is 0.3: 0: 1: 33: 0.03.
5.2 get the embodiment 5.1 described aqueous solution 10 mL, be placed in 75 ℃ the oil bath isothermal reaction 23 h.
5.3 after reaction finishes, be that the triangle sheet of 30 nm is silver nanostructured, as shown in Figure 4 through obtaining the average length of side after centrifugation and the washing.
Embodiment 6
6.1 the silver nitrate aqueous solution that is 300 mM to 2 mL concentration mixes with the aqueous solution 1 mL of cetyltrimethylammonium base amine; The aqueous solution that adds 10 mL polyvinylpyrrolidones afterwards; After the mixing and stirring; Add 0.23 mg sodium borohydride powder, obtain the uniform aqueous solution after the stirring, wherein the weight ratio of silver nitrate/sodium chloride/cetyltrimethylammonium base amine/polyvinylpyrrolidone/sodium borohydride is 0.5:0: 0.38: 20: 1.
6.2 get the embodiment 6.1 described aqueous solution 10 mL, be placed in 50 ℃ the oil bath isothermal reaction 70 h.
6.3 after reaction finishes, be that the triangle sheet of 80 nm is silver nanostructured through obtaining the average length of side after centrifugation and the washing.
Embodiment 7
7.1 the silver nitrate aqueous solution that is 2.3 mM to 6 mL concentration mixes with the aqueous solution 6 mL of natrium citricum; The aqueous solution that adds 10 mL polyvinylpyrrolidones afterwards; After the mixing and stirring; Add 0.23 mg sodium borohydride powder, obtain the uniform aqueous solution after the stirring, wherein the weight ratio of silver nitrate/sodium chloride/sodium citrate/polyvinylpyrrolidone/sodium borohydride is 0.3: 0: 1: 40: 0.03.
7.2 get the embodiment 7.1 described aqueous solution 10 mL, be placed in 75 ℃ the oil bath isothermal reaction 27 h.
7.3 after reaction finishes, be that the triangle sheet of 105 nm is silver nanostructured, as shown in Figure 5 through obtaining the average length of side after centrifugation and the washing.
Embodiment 8
8.1 the silver nitrate aqueous solution that is 6.8 mM to 6 mL concentration mixes with the aqueous solution 6 mL of natrium citricum; The aqueous solution that adds 10 mL polyvinylpyrrolidones afterwards; After the mixing and stirring; Add 0.11 mg sodium borohydride powder, obtain the uniform aqueous solution after the stirring, wherein the weight ratio of silver nitrate/sodium chloride/sodium citrate/polyvinylpyrrolidone/sodium borohydride is 0.9: 0: 1: 27: 0.01.
8.2 get the embodiment 8.1 described aqueous solution 10 mL, be placed in 75 ℃ the oil bath isothermal reaction 35 h.
8.3 after reaction finishes, be that the triangle sheet of 30 nm is silver nanostructured through obtaining the average length of side after centrifugation and the washing.
Embodiment 9
9.1 the silver nitrate aqueous solution that is 2.3 mM to 6 mL concentration mixes with the aqueous solution 6 mL of natrium citricum; The aqueous solution that adds 10 mL polyvinylpyrrolidones afterwards; After the mixing and stirring; Add 0.11 mg sodium borohydride powder, obtain the uniform aqueous solution after the stirring, wherein the weight ratio of silver nitrate/sodium chloride/sodium citrate/polyvinylpyrrolidone/sodium borohydride is 0.3: 0: 1: 53: 0.015.
9.2 get the embodiment 9.1 described aqueous solution 10 mL, be placed in 75 ℃ the oil bath isothermal reaction 31 h.
9.3 after reaction finishes, be that the triangle sheet of 24 nm is silver nanostructured, as shown in Figure 6 through obtaining the average length of side after centrifugation and the washing.
Embodiment 10
10.1 the silver nitrate aqueous solution that is 400 mM to 6 mL concentration mixes with the aqueous solution 5 mL of natrium citricum; The aqueous solution that adds 3 mL sodium chloride and polyvinylpyrrolidone afterwards; After the mixing and stirring; Add 0.1 mg sodium borohydride powder, obtain the uniform aqueous solution after the stirring, wherein the weight ratio of silver nitrate/sodium chloride/sodium citrate/polyvinylpyrrolidone/sodium borohydride is 10: 0.18: 1: 8: 0.01.
10.2 get the embodiment 10.1 described aqueous solution 8 mL, be placed in 60 ℃ the oil bath, injecting 1.5 mL concentration with the injection rate of 0.01 mL/min is 800 mM silver nitrate aqueous solutions, continues reaction 24 h.
10.3 after reaction finishes, be 20 silver-colored nanometer rods through obtaining draw ratio after centrifugation and the washing.
Embodiment 11
11.1 the silver nitrate aqueous solution that is 500 mM to 4 mL concentration mixes with the aqueous solution 4 mL of ascorbic acid; The aqueous solution that adds 6 mL sodium bromides and cetyl trimethyl amine afterwards; After the mixing and stirring; Add 0.4 mg sodium borohydride powder, obtain the uniform aqueous solution after the stirring, wherein the weight ratio of silver nitrate/sodium bromide/ascorbic acid/cetyl trimethyl amine/sodium borohydride is 10: 0.1: 1: 10: 0.02.
11.2 get the embodiment 11.1 described aqueous solution 8 mL, be placed in 80 ℃ the oil bath, injecting 2 mL concentration with the injection rate of 0.01 mL/min is 100 mM silver nitrate aqueous solutions, continues reaction 44 h.
11.3 after reaction finishes, be 40 silver-colored nanometer rods through obtaining draw ratio after centrifugation and the washing.
Embodiment 12
12.1 the silver nitrate aqueous solution that is 170 mM to 6 mL concentration mixes with the aqueous solution 3 mL of natrium citricum; The aqueous solution that adds 4 mL KBrs and vinyl pyrrolidone afterwards; After the mixing and stirring; Add 0.2 mg sodium borohydride powder, obtain the uniform aqueous solution after the stirring, wherein the weight ratio of silver nitrate/KBr/natrium citricum/vinyl pyrrolidone/sodium borohydride is 3.4: 0.08: 1.2: 1: 0.004.
12.2 get the embodiment 12.1 described aqueous solution 10 mL, be placed in 100 ℃ the oil bath, injecting 0.8 mL concentration with the injection rate of 0.01 mL/min is 500 mM silver nitrate aqueous solutions, continues reaction 28 h.
After 12.3 reaction finishes, through obtaining the silver-colored nanometer rods that draw ratio is 80 nm after centrifugation and the washing.
Embodiment 13
13.1 the silver nitrate aqueous solution that is 100 mM to 6 mL concentration mixes with the aqueous solution 4 mL of ascorbic acid; The aqueous solution that adds 6 mL sodium iodides and polyvinylpyrrolidone afterwards; After the mixing and stirring; Add 0.2 mg sodium borohydride powder, obtain the uniform aqueous solution after the stirring, wherein the weight ratio of silver nitrate/sodium iodide/ascorbic acid/polyvinylpyrrolidone/sodium borohydride is 2: 0.036: 1: 6: 0.004.
13.2 get the embodiment 13.1 described aqueous solution 6 mL, be placed in 60 ℃ the oil bath, injecting 1.0 mL concentration with the injection rate of 0.01 mL/min is 70 mM silver nitrate aqueous solutions, continues reaction 46 h.
After 13.3 reaction finishes, through obtaining the nano silver wire that diameter is 300 nm after centrifugation and the washing.
Embodiment 14
14.1 the silver nitrate aqueous solution that is 200 mM to 5 mL concentration mixes with the aqueous solution 10 mL of ascorbic acid; The aqueous solution that adds 2 mL potassium chloride and polyvinylpyrrolidone afterwards; After the mixing and stirring; Add 2 mg sodium borohydride powder, obtain the uniform aqueous solution after the stirring, wherein the weight ratio of silver nitrate/potassium chloride/ascorbic acid/polyvinylpyrrolidone/sodium borohydride is 0.34: 0.004: 0.02: 1: 0.004.
14.2 get the embodiment 14.1 described aqueous solution 10 mL, be placed in 100 ℃ the oil bath, injecting 2.0 mL concentration with the injection rate of 0.01 mL/min is 30 mM silver nitrate aqueous solutions, continues reaction 10 h.
After 14.3 reaction finishes, through obtaining the nano silver wire that diameter is 100 nm after centrifugation and the washing.
Embodiment 15
15.1 the silver nitrate aqueous solution that is 200 mM to 5 mL concentration mixes with the aqueous solution 10 mL of ascorbic acid; The aqueous solution that adds 2 mL potassium chloride and polyvinylpyrrolidone afterwards; After the mixing and stirring; Add 2 mg sodium borohydride powder, obtain the uniform aqueous solution after the stirring, wherein the weight ratio of silver nitrate/potassium chloride/ascorbic acid/polyvinylpyrrolidone/sodium borohydride is 0.34: 0.004: 0.02: 1.7: 0.004.
15.2 get the embodiment 15.1 described aqueous solution 8 mL, be placed in 80 ℃ the oil bath, injecting 1.0 mL concentration with the injection rate of 0.01 mL/min is 300 mM silver nitrate aqueous solutions, continues reaction 31 h.
After 15.3 reaction finishes, through obtaining the nano silver wire that diameter is 50 nm after centrifugation and the washing.
Embodiment 16
16.1 is 6 mL concentration that 300 mM silver nitrate aqueous solutions mix with the aqueous solution 2 mL of cetyltrimethylammonium base amine; The aqueous solution that adds 4 mL KIs and 2-Pyrrolidone afterwards; After the mixing and stirring; Add the sodium borohydride powder of 4 mg, obtain the uniform aqueous solution after the stirring, wherein the weight ratio of silver nitrate/KI/cetyltrimethylammonium base amine/2-Pyrrolidone/sodium borohydride is 3.8: 0.04: 2.5: 1: 0.05.
16.2 get embodiment 16.1 described initial condition solution 10 mL, be placed in 60 ℃ the oil bath, injecting 2 mL concentration with the injection rate of 1 mL/min is 500 mM silver nitrate aqueous solutions, continues reaction 60 h.
After 16.3 reaction finishes, through obtaining the silver-colored nano cubic block that the length of side is 120 nm after centrifugation and the washing.
Embodiment 17
17.1 is 6 mL concentration that 50 mM silver nitrate aqueous solutions mix with the aqueous solution 6 mL of natrium citricum; The aqueous solution that adds 10 mL potassium chloride and polyvinylpyrrolidone afterwards; After the mixing and stirring; Add the sodium borohydride powder of 2 mg, obtain the uniform aqueous solution after the stirring, wherein the weight ratio of silver nitrate/potassium chloride/natrium citricum/polyvinylpyrrolidone/sodium borohydride is 2.6: 0.09: 2: 1: 0.1.
17.2 get the embodiment 17.1 described aqueous solution 10 mL, be placed in 100 ℃ the oil bath, injecting 1.0 mL concentration with the injection rate of 1 mL/min is 100 mM silver nitrate aqueous solutions, continues reaction 30 h.
After 17.3 reaction finishes, through obtaining the silver-colored nano cubic block that the length of side is 90 nm after centrifugation and the washing.
Embodiment 18
18.1 is 3 mL concentration that 30 mM silver nitrate aqueous solutions mix with the aqueous solution 5 mL of ascorbic acid; The aqueous solution that adds 4 mL sodium chloride and polyvinylpyrrolidone afterwards; After the mixing and stirring; Add the sodium borohydride powder of 1 mg, obtain the uniform aqueous solution after the stirring, wherein the weight ratio of silver nitrate/sodium chloride/ascorbic acid/polyvinylpyrrolidone/sodium borohydride is 8.3: 1: 8.3: 5.5: 0.5.
18.2 get the embodiment 18.1 described aqueous solution 10 mL, be placed in 90 ℃ the oil bath, injecting 0.8 mL concentration with the injection rate of 1 mL/min is 800 mM silver nitrate aqueous solutions, continues reaction 40 h.
After 18.3 reaction finishes, through obtaining the silver-colored nano cubic block that the length of side is 60 nm after centrifugation and the washing.
Claims (8)
1. method that in the aqueous solution, prepares the argent nanostructured is characterized in that may further comprise the steps:
(1) preparation of the predecessor aqueous solution: with silver nitrate aqueous solution and reproducibility compound, add alkali halide and pyrrolidones stabilizing agent then, add sodium borohydride after stirring again, stir and obtain the uniform precursor aqueous solution;
(2) silver nanostructured growth: adopt in following a or the b method any to continue to handle predecessor aqueous solution, preparation different-shape silver nanostructured:
A. with the predecessor aqueous solution of step (1) at 50～105 ℃ of following isothermal reaction 3～100 h;
B. get the described predecessor aqueous solution of step (1), keep its temperature, slowly inject silver nitrate aqueous solution then, inject continued reaction 5～50 h that finish at 50～105 ℃;
(3) after step (2) reaction finishes,, obtain the silver nanostructured of different-shape with reactant liquor centrifugation, washing.
2. preparation method according to claim 1 is characterized in that: said reproducibility compound is natrium citricum, ascorbic acid or cetyltrimethylammonium base amine; Said pyrrolidones stabilizing agent is polyvinylpyrrolidone, N-methyl pyrrolidone, vinyl pyrrolidone or 2-Pyrrolidone; Said alkali halide is sodium chloride, potassium chloride, sodium bromide, KBr, sodium iodide or KI.
3. preparation method according to claim 1 and 2 is characterized in that: in the step (1), said reproducibility compound, pyrrolidones stabilizing agent and alkali halide add with the form of the aqueous solution.
4. preparation method according to claim 1; It is characterized in that: in the step (1), silver nitrate: alkali halide: reproducibility compound: pyrrolidones: the mass ratio of sodium borohydride is 0.1～10: 0～6: 0～10: 1～100: 0.001～1.
5. preparation method according to claim 1 is characterized in that: in the step (1), the concentration of silver nitrate aqueous solution is 1～5 * 10 in the predecessor aqueous solution
2Mmol/L, the reproducibility compound concentrations is 0～9 * 10
2Mmol/L, the concentration of alkali halide is 0～2 * 10
2Mmol/L, the concentration of pyrrolidones stabilizing agent is 0～7 * 10
4Mmol/L.
6. preparation method according to claim 1 is characterized in that: among the step b, the injection rate of silver nitrate aqueous solution is 0.01mL/min, and the concentration of silver nitrate aqueous solution is 1～10 * 10
3Mmol/L, the mass ratio of silver nitrate is 1:2～16 in the silver nitrate and the predecessor aqueous solution.
7. preparation method according to claim 1 is characterized in that: among the step b, the injection rate of silver nitrate is 1mL/min, and the concentration of silver nitrate aqueous solution is 1～10 * 10
3Mmol/L, the mass ratio of silver nitrate is 1:0.01～3 in the silver nitrate and the predecessor aqueous solution.
8. preparation method according to claim 1 is characterized in that: said silver nanostructured pattern is sphere, triangle sheet, cube bulk, nano bar-shape or nanometer wire.
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