CN102554258B - 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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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 60
- 239000004332 silver Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000002086 nanomaterial Substances 0.000 title abstract description 10
- 229910052751 metal Inorganic materials 0.000 title description 3
- 239000002184 metal Substances 0.000 title description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 2
- 239000007864 aqueous solution Substances 0.000 claims abstract description 141
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 239000000376 reactant Substances 0.000 claims abstract description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 148
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 74
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 44
- 239000012279 sodium borohydride Substances 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 40
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 34
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 30
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 30
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 28
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 25
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 20
- 238000005119 centrifugation Methods 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 239000011780 sodium chloride Substances 0.000 claims description 17
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 15
- 150000004820 halides Chemical class 0.000 claims description 15
- 238000002347 injection Methods 0.000 claims description 15
- 239000007924 injection Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 150000004040 pyrrolidinones Chemical class 0.000 claims description 12
- 239000003381 stabilizer Substances 0.000 claims description 12
- 239000001103 potassium chloride Substances 0.000 claims description 10
- 235000011164 potassium chloride Nutrition 0.000 claims description 10
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 10
- 235000010323 ascorbic acid Nutrition 0.000 claims description 8
- 239000011668 ascorbic acid Substances 0.000 claims description 8
- 229960005070 ascorbic acid Drugs 0.000 claims description 8
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 4
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 4
- 235000009518 sodium iodide Nutrition 0.000 claims description 4
- 238000002156 mixing Methods 0.000 abstract description 20
- 239000000243 solution Substances 0.000 abstract description 6
- 239000002243 precursor Substances 0.000 abstract description 4
- 239000011261 inert gas Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 description 18
- 239000000843 powder Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 14
- 239000001509 sodium citrate Substances 0.000 description 8
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 8
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 6
- 229930003268 Vitamin C Natural products 0.000 description 6
- 239000011260 aqueous acid Substances 0.000 description 6
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- 239000002245 particle Substances 0.000 description 6
- 235000019154 vitamin C Nutrition 0.000 description 6
- 239000011718 vitamin C Substances 0.000 description 6
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- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
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- 241000792859 Enema Species 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N anhydrous trimethylamine Natural products CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000000090 biomarker Substances 0.000 description 2
- -1 cetyl trimethyl amine Chemical compound 0.000 description 2
- 230000013872 defecation Effects 0.000 description 2
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Abstract
本发明公开了一种在水溶液里制备金属银纳米结构的方法，步骤包括：根据不同形貌的要求确定起始反应物的种类及比例，混合均匀制得前驱物水溶液；将前驱物水溶液在50～105℃恒温下生长银纳米结构；将反应液离心分离、洗涤，得不同形貌的银纳米结构。本发明无需通入惰性气体保护，反应温度低，制备过程简单、成本低，克服了传统的多羟基还原法、光照法、氧化还原法中存在的制备程序复杂、产量低、成本高等不足，对不同形貌的银纳米结构的大批量工业化生产及其实际应用具有重要意义。
The invention discloses a method for preparing metallic silver nanostructures in an aqueous solution. The steps include: determining the type and proportion of starting reactants according to the requirements of different shapes, and mixing uniformly to obtain a precursor aqueous solution; mixing the precursor aqueous solution at 50 Silver nanostructures are grown at a constant temperature of ~105°C; the reaction solution is centrifuged and washed to obtain silver nanostructures with different shapes. The invention does not need to be protected by inert gas, the reaction temperature is low, the preparation process is simple, and the cost is low. The large-scale industrial production and practical application of silver nanostructures with different morphologies are of great significance.
Description
Technical field
The present invention relates to a kind of method of preparing argent nanostructured in the aqueous solution, belong to Nano Silver preparing technical field.
Background technology
Different-shape silver nanostructured because its potential application at nanoelectronics, magnetics, biology sensor, data storage, catalysis, SERS and the aspect such as antibacterial 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 increasingly microminiaturized and the 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 controlled silver nanostructured preparation of pattern and size seems very important.For example, the particle diameter of spherical silver nano particle is little, narrow particle size distribution, is the material with satisfactory electrical conductivity, can be used as good electrode material.Therefore, prepare regular spherical silver nano material, very crucial to the performance of raising battery.But at present less about the report of the controlled silver nanoparticle ball of preparation size, therefore the synthetic controlled silver nanoparticle ball of 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 larger, surface can be lower, non-oxidizability is strong, more stable than the nanostructured of other pattern, there is great using value in fields such as catalysis, SERS, metal-enhanced fluorescence spectrum, infrared therapeutic, biomarker, nano conductive adhesive electronic package materials.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 that current low cost is prepared Nano silver piece.For example, Roh (Langmuir 2010,26 (14), 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).It is silver nanostructured that the stable photochemical method of Stamplecoskie (J. AM. CHEM. SOC. 2010,132,1825-1827) 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, Syntheses in water, to such silver nanostructured synthetic simple approach efficiently that provides, has cost low, environmental protection, the advantage such as economize on resources, and preparation process favorable repeatability, easily control.
Summary of the invention
, the shortcoming such as size single, complicated operation irregular for the nanoscale silver existing in prior art; the invention provides a kind of method of preparing argent nanostructured in the aqueous solution; the method can be prepared pattern, argent nanostructured that size is adjustable; simple to operate, do not need inert gas shielding, reaction temperature low, reproducible.
The present invention utilizes the silver nanostructured of the synthetic different-shape of sodium borohydride reduction one step preparation, and reaction is carried out in the aqueous solution, and process is simple, reproducible, and concrete technical scheme is as follows:
A method of preparing argent nanostructured in the aqueous solution, comprises the following steps:
(1) preparation of the predecessor aqueous solution: by silver nitrate aqueous solution and reproducibility compound, then add alkali halide and pyrrolidones stabilizing agent, add again sodium borohydride after stirring, stir and obtain the uniform predecessor aqueous solution;
(2) silver nanostructured growth: adopt any continuation in following a or b method to process the predecessor aqueous solution, prepare the silver nanostructured of different-shape:
A. by the predecessor aqueous solution of step (1) isothermal reaction 3～100 h at 50～105 ℃;
B. get the described predecessor aqueous solution of step (1), keep its temperature at 50～105 ℃, then slowly inject silver nitrate aqueous solution, after injection, continue reaction 5～50 h;
(3) after step (2) reaction finishes, by reactant liquor centrifugation, washing, obtain the silver nanostructured of different-shape.
In above-mentioned preparation method, described reproducibility compound is natrium citricum, ascorbic acid or cetyltrimethylammonium base amine; Described pyrrolidones stabilizing agent is polyvinylpyrrolidone, 1-METHYLPYRROLIDONE, vinyl pyrrolidone or 2-Pyrrolidone; Described alkali halide is sodium chloride, potassium chloride, sodium bromide, KBr, sodium iodide or KI.
In above-mentioned preparation method, in 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.
In above-mentioned preparation method, take silver nitrate, reproducibility compound, pyrrolidones, alkali halide, sodium borohydride as reactant, be made into the predecessor aqueous solution, reaction is carried out in the aqueous solution, for each material is mixed, except 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 a certain impact to the pattern of end product, considers the unicity of end product pattern, the uniformity of size, and in step (1), in the predecessor aqueous solution, the concentration of silver nitrate is preferably 1～5 × 10
2mmol/L, the concentration of reproducibility compound 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 growth by two kinds of forms, one is that the predecessor aqueous solution does not add any reagent, directly under the temperature and time of setting, react, grow silver nanostructured, another kind is in the predecessor aqueous solution, to continue to add silver nitrate aqueous solution, and then react under the temperature and time of setting, grow silver nanostructured.Wherein silver nitrate aqueous solution adds in the predecessor aqueous solution in two ways, one 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 injecting that the silver nitrate injecting reaches with the mass ratio of predecessor aqueous solution silver nitrate, and the concentration of silver nitrate aqueous solution used 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 injecting that the silver nitrate injecting reaches with the mass ratio of predecessor aqueous solution silver nitrate, and the concentration of silver nitrate aqueous solution used is 1～10 × 10
3mmol/L.
The silver nanostructured pattern of the present invention mainly determined by the amount ratio of the initial reactants such as reproducibility compound, stabilizing agent, alkali halide, and the silver nanostructured pattern of gained is spherical, triangle sheet, cube bulk, nano bar-shape, nanometer wire etc.
In the time that 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 larger to the silver nanostructured particle size of gained and size impact, silver nanostructured size Control reaction temperature and time that in the preparation can be according to actual needs.Within the scope of technical solution of the present invention, the diameter of silver nanoparticle ball in about 3-100 nm, the silver nanostructured length of side of triangle sheet in 10-150 nm left and right, the silver nanostructured length of side of cube bulk is in the draw ratio of 50-200 nm left and right, silver nanoparticle rod and nano silver wire in 3-100 left and right, diameter is in 10-500 nm left and right.
This method is by controlling reproducibility compound, stabilizing agent, the impact of alkali halide on silver nanostructured growth kinetics, the synthetic argent nanostructured with various patterns, due to these silver nanostructured narrow particle size distributions, granularity is adjustable, electric conductivity is good, can be used as good electrode material, there is 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 Nano Silver structure; reaction is carried out in the aqueous solution; adopt the silver nanostructured patterns of material control such as stabilizing agent; without passing into inert gas shielding; reaction temperature is low; preparation process is simple, output is high, cost is low; overcome the preparation procedure complexity that exists in the methods such as crystal seed method, luminescence method, traditional polyhydroxy reducing process, yielded poorly, high in cost of production deficiency, thereby the present invention is by significant to the mass industrialized production to silver nanostructured and practical application thereof.
Accompanying drawing explanation
Fig. 1 is transmission electron microscope photo (TEM) picture of the synthetic silver nanoparticle ball of the embodiment of the present invention 1.
Fig. 2 is transmission electron microscope photo (TEM) picture of the synthetic silver nanoparticle ball of the embodiment of the present invention 2.
Fig. 3 is transmission electron microscope photo (TEM) picture of the synthetic silver nanoparticle ball of the embodiment of the present invention 4.
Fig. 4 is transmission electron microscope photo (TEM) picture of the synthetic Nano silver piece of the embodiment of the present invention 5.
Fig. 5 is transmission electron microscope photo (TEM) picture of the synthetic Nano silver piece of the embodiment of the present invention 7.
Fig. 6 is transmission electron microscope photo (TEM) picture of the synthetic Nano silver piece of the embodiment of the present invention 9.
The specific embodiment
Below by embodiment, the present invention will be further elaborated, should be understood that, following explanation is only in order to explain the present invention, its content is not limited.
embodiment 1
1.1 3 mL concentration are that the silver nitrate aqueous solution of 30 mM and the aqueous solution of natrium citricum 10 mL mix, add afterwards the aqueous solution of 3 mL sodium chloride and polyvinylpyrrolidone, after mixing and stirring, add 1.5 mg sodium borohydride powder, after stirring, obtain the uniform aqueous solution, 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 aqueous solution 10 mL described in embodiment 1.1, are placed in the oil bath of 100 ℃ isothermal reaction 32 h.
After 1.3 reactions finish, after centrifugation and washing, obtain the silver nanoparticle ball that average diameter is 23 nm, as shown in Figure 1.
2.1 2 mL concentration are that the silver nitrate aqueous solution of 450 mM and the aqueous solution of natrium citricum 10 mL mix, add afterwards the aqueous solution of 3 mL sodium chloride and polyvinylpyrrolidone, after mixing and stirring, add 1.5 mg sodium borohydride powder, after stirring, obtain the uniform aqueous solution, 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 aqueous solution 10 mL described in embodiment 2.1, are placed in the oil bath of 90 ℃ isothermal reaction 26 h.
After 2.3 reactions finish, after centrifugation and washing, obtain the silver nanoparticle ball that average diameter is 8.5 nm, as shown in Figure 2.
embodiment 3
3.1 0.6 mL concentration are that 100 mM silver nitrate aqueous solutions mix with Vitamin C aqueous acid 12 mL, add afterwards the aqueous solution of 2 mL potassium chloride and 1-METHYLPYRROLIDONE, after mixing and stirring, add 1.5 mg sodium borohydride powder, after stirring, obtain the uniform aqueous solution, wherein the weight of silver nitrate/potassium chloride/ascorbic acid/1-METHYLPYRROLIDONE/sodium borohydride is 6: 1: 5: 7: 0.5.
3.2 get the aqueous solution 10 mL described in embodiment 3.1, are placed in the oil bath of 80 ℃ isothermal reaction 40 h.
After 3.3 reactions finish, after centrifugation and washing, obtain the silver nanoparticle ball that average diameter is 80 nm.
embodiment 4
4.1 1 mL concentration are that the silver nitrate aqueous solution of 90 mM and the aqueous solution of natrium citricum 5 mL mix, add afterwards the aqueous solution of 5 mL sodium chloride and polyvinylpyrrolidone, after mixing and stirring, add 1.5 mg sodium borohydride powder, after stirring, obtain the uniform aqueous solution, 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 aqueous solution 10 mL described in embodiment 4.1, are placed in the oil bath of 100 ℃ isothermal reaction 6 h.
After 4.3 reactions finish, after centrifugation and washing, obtain the silver nanoparticle ball that average diameter is 6 nm, as shown in Figure 3.
embodiment 5
5.1 6 mL concentration are that the silver nitrate aqueous solution of 2.3 mM and the aqueous solution of natrium citricum 10 mL mix, add afterwards the aqueous solution of 4 mL polyvinylpyrrolidones, after mixing and stirring, add 0.23 mg sodium borohydride powder, after stirring, obtain the uniform aqueous solution, 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 aqueous solution 10 mL described in embodiment 5.1, are placed in the oil bath of 75 ℃ isothermal reaction 23 h.
After 5.3 reactions finish, after centrifugation and washing, obtaining the average length of side is that the triangle sheet of 30 nm is silver nanostructured, as shown in Figure 4.
embodiment 6
The silver nitrate aqueous solution that 6.1 2 mL concentration are 300 mM mixes with the aqueous solution 1 mL of cetyltrimethylammonium base amine, add afterwards the aqueous solution of 10 mL polyvinylpyrrolidones, after mixing and stirring, add 0.23 mg sodium borohydride powder, after stirring, obtain the uniform aqueous solution, the weight ratio of wherein silver nitrate/sodium chloride/cetyltrimethylammonium base amine/polyvinylpyrrolidone/sodium borohydride is 0.5:0: 0.38: 20: 1.
6.2 get the aqueous solution 10 mL described in embodiment 6.1, are placed in the oil bath of 50 ℃ isothermal reaction 70 h.
After 6.3 reactions finish, after centrifugation and washing, obtaining the average length of side is that the triangle sheet of 80 nm is silver nanostructured.
7.1 6 mL concentration are that the silver nitrate aqueous solution of 2.3 mM and the aqueous solution of natrium citricum 6 mL mix, add afterwards the aqueous solution of 10 mL polyvinylpyrrolidones, after mixing and stirring, add 0.23 mg sodium borohydride powder, after stirring, obtain the uniform aqueous solution, 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 aqueous solution 10 mL described in embodiment 7.1, are placed in the oil bath of 75 ℃ isothermal reaction 27 h.
After 7.3 reactions finish, after centrifugation and washing, obtaining the average length of side is that the triangle sheet of 105 nm is silver nanostructured, as shown in Figure 5.
embodiment 8
8.1 6 mL concentration are that the silver nitrate aqueous solution of 6.8 mM and the aqueous solution of natrium citricum 6 mL mix, add afterwards the aqueous solution of 10 mL polyvinylpyrrolidones, after mixing and stirring, add 0.11 mg sodium borohydride powder, after stirring, obtain the uniform aqueous solution, 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 aqueous solution 10 mL described in embodiment 8.1, are placed in the oil bath of 75 ℃ isothermal reaction 35 h.
After 8.3 reactions finish, after centrifugation and washing, obtaining the average length of side is that the triangle sheet of 30 nm is silver nanostructured.
embodiment 9
9.1 6 mL concentration are that the silver nitrate aqueous solution of 2.3 mM and the aqueous solution of natrium citricum 6 mL mix, add afterwards the aqueous solution of 10 mL polyvinylpyrrolidones, after mixing and stirring, add 0.11 mg sodium borohydride powder, after stirring, obtain the uniform aqueous solution, 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 aqueous solution 10 mL described in embodiment 9.1, are placed in the oil bath of 75 ℃ isothermal reaction 31 h.
After 9.3 reactions finish, after centrifugation and washing, obtaining the average length of side is that the triangle sheet of 24 nm is silver nanostructured, as shown in Figure 6.
embodiment 10
10.1 6 mL concentration are that the silver nitrate aqueous solution of 400 mM and the aqueous solution of natrium citricum 5 mL mix, add afterwards the aqueous solution of 3 mL sodium chloride and polyvinylpyrrolidone, after mixing and stirring, add 0.1 mg sodium borohydride powder, after stirring, obtain the uniform aqueous solution, 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 aqueous solution 8 mL described in embodiment 10.1, are placed in the oil bath of 60 ℃, inject 1.5 mL concentration as 800 mM silver nitrate aqueous solutions take the injection rate of 0.01 mL/min, continue reaction 24 h.
After 10.3 reactions finish, after centrifugation and washing, obtaining draw ratio is 20 silver nanoparticle rod.
embodiment 11
The silver nitrate aqueous solution that 11.1 4 mL concentration are 500 mM mixes with Vitamin C aqueous acid 4 mL, add afterwards the aqueous solution of 6 mL sodium bromides and cetyl trimethyl amine, after mixing and stirring, add 0.4 mg sodium borohydride powder, after stirring, obtain the uniform aqueous solution, the weight ratio of wherein silver nitrate/sodium bromide/ascorbic acid/cetyl trimethyl amine/sodium borohydride is 10: 0.1: 1: 10: 0.02.
11.2 get the aqueous solution 8 mL described in embodiment 11.1, are placed in the oil bath of 80 ℃, inject 2 mL concentration as 100 mM silver nitrate aqueous solutions take the injection rate of 0.01 mL/min, continue reaction 44 h.
After 11.3 reactions finish, after centrifugation and washing, obtaining draw ratio is 40 silver nanoparticle rod.
embodiment 12
12.1 6 mL concentration are that the silver nitrate aqueous solution of 170 mM and the aqueous solution of natrium citricum 3 mL mix, add afterwards the aqueous solution of 4 mL KBrs and vinyl pyrrolidone, after mixing and stirring, add 0.2 mg sodium borohydride powder, after stirring, obtain the uniform aqueous solution, 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 aqueous solution 10 mL described in embodiment 12.1, are placed in the oil bath of 100 ℃, inject 0.8 mL concentration as 500 mM silver nitrate aqueous solutions take the injection rate of 0.01 mL/min, continue reaction 28 h.
After 12.3 reactions finish, after centrifugation and washing, obtain the silver nanoparticle rod that draw ratio is 80 nm.
embodiment 13
The silver nitrate aqueous solution that 13.1 6 mL concentration are 100 mM mixes with Vitamin C aqueous acid 4 mL, add afterwards the aqueous solution of 6 mL sodium iodides and polyvinylpyrrolidone, after mixing and stirring, add 0.2 mg sodium borohydride powder, after stirring, obtain the uniform aqueous solution, 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 aqueous solution 6 mL described in embodiment 13.1, are placed in the oil bath of 60 ℃, inject 1.0 mL concentration as 70 mM silver nitrate aqueous solutions take the injection rate of 0.01 mL/min, continue reaction 46 h.
After 13.3 reactions finish, after centrifugation and washing, obtain the nano silver wire that diameter is 300 nm.
embodiment 14
The silver nitrate aqueous solution that 14.1 5 mL concentration are 200 mM mixes with Vitamin C aqueous acid 10 mL, add afterwards the aqueous solution of 2 mL potassium chloride and polyvinylpyrrolidone, after mixing and stirring, add 2 mg sodium borohydride powder, after stirring, obtain the uniform aqueous solution, 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 aqueous solution 10 mL described in embodiment 14.1, are placed in the oil bath of 100 ℃, inject 2.0 mL concentration as 30 mM silver nitrate aqueous solutions take the injection rate of 0.01 mL/min, continue reaction 10 h.
After 14.3 reactions finish, after centrifugation and washing, obtain the nano silver wire that diameter is 100 nm.
embodiment 15
The silver nitrate aqueous solution that 15.1 5 mL concentration are 200 mM mixes with Vitamin C aqueous acid 10 mL, add afterwards the aqueous solution of 2 mL potassium chloride and polyvinylpyrrolidone, after mixing and stirring, add 2 mg sodium borohydride powder, after stirring, obtain the uniform aqueous solution, 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 aqueous solution 8 mL described in embodiment 15.1, are placed in the oil bath of 80 ℃, inject 1.0 mL concentration as 300 mM silver nitrate aqueous solutions take the injection rate of 0.01 mL/min, continue reaction 31 h.
After 15.3 reactions finish, after centrifugation and washing, obtain the nano silver wire that diameter is 50 nm.
embodiment 16
16.1 6 mL concentration are that 300 mM silver nitrate aqueous solutions mix with the aqueous solution 2 mL of cetyltrimethylammonium base amine, add afterwards the aqueous solution of 4 mL KIs and 2-Pyrrolidone, after mixing and stirring, add the sodium borohydride powder of 4 mg, after stirring, obtain the uniform aqueous solution, the weight ratio of wherein silver nitrate/KI/cetyltrimethylammonium base amine/2-Pyrrolidone/sodium borohydride is 3.8: 0.04: 2.5: 1: 0.05.
16.2 get initial condition solution 10 mL described in embodiment 16.1, are placed in the oil bath of 60 ℃, inject 2 mL concentration as 500 mM silver nitrate aqueous solutions take the injection rate of 1 mL/min, continue reaction 60 h.
After 16.3 reactions finish, after centrifugation and washing, obtain the silver nanoparticle cubic block that the length of side is 120 nm.
embodiment 17
17.1 6 mL concentration are that 50 mM silver nitrate aqueous solutions mix with the aqueous solution 6 mL of natrium citricum, add afterwards the aqueous solution of 10 mL potassium chloride and polyvinylpyrrolidone, after mixing and stirring, add the sodium borohydride powder of 2 mg, after stirring, obtain the uniform aqueous solution, 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 aqueous solution 10 mL described in embodiment 17.1, are placed in the oil bath of 100 ℃, inject 1.0 mL concentration as 100 mM silver nitrate aqueous solutions take the injection rate of 1 mL/min, continue reaction 30 h.
After 17.3 reactions finish, after centrifugation and washing, obtain the silver nanoparticle cubic block that the length of side is 90 nm.
embodiment 18
18.1 3 mL concentration are that 30 mM silver nitrate aqueous solutions mix with Vitamin C aqueous acid 5 mL, add afterwards the aqueous solution of 4 mL sodium chloride and polyvinylpyrrolidone, after mixing and stirring, add the sodium borohydride powder of 1 mg, after stirring, obtain the uniform aqueous solution, 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 aqueous solution 10 mL described in embodiment 18.1, are placed in the oil bath of 90 ℃, inject 0.8 mL concentration as 800 mM silver nitrate aqueous solutions take the injection rate of 1 mL/min, continue reaction 40 h.
After 18.3 reactions finish, after centrifugation and washing, obtain the silver nanoparticle cubic block that the length of side is 60 nm.
Claims (6)
1. a method of preparing argent nanostructured in the aqueous solution, is characterized in that comprising the following steps:
(1) preparation of the predecessor aqueous solution: by silver nitrate aqueous solution and reproducibility compound, then add alkali halide and pyrrolidones stabilizing agent, add again sodium borohydride after stirring, stir and obtain the uniform predecessor aqueous solution;
(2) silver nanostructured growth: adopt any continuation in following a or b method to process the predecessor aqueous solution, prepare the silver nanostructured of different-shape:
A. by the predecessor aqueous solution of step (1) isothermal reaction 3～100 h at 50～105 ℃;
B. get the described predecessor aqueous solution of step (1), keep its temperature at 50～105 ℃, then slowly inject silver nitrate aqueous solution, after injection, continue reaction 5～50 h;
(3) after step (2) reaction finishes, by reactant liquor centrifugation, washing, obtain the silver nanostructured of different-shape;
In step (1), silver nitrate: alkali halide: reproducibility compound: pyrrolidones stabilizing agent: the mass ratio of sodium borohydride is 0.1～10: 0～6: 0～10: 1～100: 0.001～1, wherein the consumption of alkali halide and reproducibility compound is all non-vanishing;
In step (1), in the predecessor aqueous solution, the concentration of silver nitrate is 1～500 mmol/L, the concentration of reproducibility compound is 0～900 mmol/L, the concentration of alkali halide is 0～200 mmol/L, the concentration of pyrrolidones stabilizing agent is 0～70000 mmol/L, and wherein the concentration of alkali halide and pyrrolidones stabilizing agent is all non-vanishing.
2. preparation method according to claim 1, is characterized in that: described reproducibility compound is natrium citricum, ascorbic acid or cetyltrimethylammonium base amine; Described pyrrolidones stabilizing agent is polyvinylpyrrolidone, 1-METHYLPYRROLIDONE, vinyl pyrrolidone or 2-Pyrrolidone; Described 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 step (1), described 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 step b, the injection rate of silver nitrate aqueous solution is 0.01mL/min, and the concentration of silver nitrate aqueous solution is 1～10000 mmol/L, and in silver nitrate and the predecessor aqueous solution, the mass ratio of silver nitrate is 1:2～16.
5. preparation method according to claim 1, it is characterized in that: in step b, the injection rate of silver nitrate aqueous solution is 1mL/min, and the concentration of silver nitrate aqueous solution is 1～10000 mmol/L, and in silver nitrate and the predecessor aqueous solution, the mass ratio of silver nitrate is 1:0.01～3.
6. preparation method according to claim 1, is characterized in that: described silver nanostructured pattern is spherical, triangle sheet, cube bulk, nano bar-shape or nanometer wire.
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