CN102806358A - Synthesis method of water-soluble monodisperse spherical silver nanocrystals - Google Patents
Synthesis method of water-soluble monodisperse spherical silver nanocrystals Download PDFInfo
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- CN102806358A CN102806358A CN2012103152350A CN201210315235A CN102806358A CN 102806358 A CN102806358 A CN 102806358A CN 2012103152350 A CN2012103152350 A CN 2012103152350A CN 201210315235 A CN201210315235 A CN 201210315235A CN 102806358 A CN102806358 A CN 102806358A
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Abstract
A synthesis method of water-soluble monodisperse spherical silver nanocrystals includes steps of firstly, preparing solution from a required raw material, namely sodium citrate, additives and soluble silver salt with high-purity water; weighing vitamin-C solution, sodium citrate solution, additive solution and soluble sliver salt solution according to the volume ratio of (5-20):100:(3-5):25, adding the vitamin-C solution into boiling water, and mixing the sodium citrate solution, additive solution and soluble silver solution for 3-6 minutes and then adding the mixture into the boiling water containing vitamin-C; and finally keeping the water boiling, heating and refluxing for one hour, and then cooling the solution to the room temperature so as to obtain the monodisperse spherical sliver nanocrystals. Compared with the other synthesis method, the synthesis method is simple in operation and capable of preparing high-quality water-soluble monodisperse spherical sliver nanocrystals which are incapable of being prepared by other conventional methods.
Description
Technical field
The present invention relates to a kind of synthetic method of water-soluble mono dispersing ball silver nanocrystal, specifically utilize the auxiliary natrium citricum reduction soluble silver salt of additive to prepare the method for water-soluble mono dispersing ball silver nanocrystal.
Background technology
In the silver-colored nanocrystal of all patterns, have only the spherical silver nanocrystal to go for the Mie theory.The Mie theory provides a kind of method of the Maxwell of analysis equation.In addition, the spherical silver nanocrystal also has many application, SERS for example, unimolecule mark and identification etc.In the method for countless synthesizing spherical silver nanocrystals, only in organic solvent, just can obtain monodisperse spherical silver nanocrystal at present.But poisonous organic solvent and organic ligand, be unfavorable for they in Application for Field such as biologies.At present, preparation spherical silver nanocrystal still is a difficult point, the particularly diameter dimension spherical silver nanocrystal greater than 10 nanometers in the aqueous solution.Because the preparation of water-soluble, monodispersed spherical silver nanocrystal difficulty also can't realize the quantitative analysis of silver-colored nanocrystal pair cell toxicity research now.Natrium citricum is a kind of biocompatibility part, and easily by replacements such as other biological molecule, antibody, therefore, the stable spherical silver nanocrystal of natrium citricum part has vast application prospect.
At present; Prepare in the whole bag of tricks of monodispersed spherical silver nanocrystal at natrium citricum reduction soluble silver salt; Although simple to operate and since silver growth characteristic, the product that obtains often different-shape silver-colored nanocrystal (for example; Bar-shaped, triangular plate and elliposoidal) mix products.Although in the document that has, obtain monodispersed spherical silver nanocrystal through using laser light to decompose auxiliary law, be not suitable for production in enormous quantities.
Summary of the invention
The present invention is directed to existing natrium citricum reduction soluble silver salt and prepare the deficiency of monodispersed spherical silver nanocrystal, the synthetic method of simple, the synthetic silver of water-soluble mono dispersing ball efficiently of a kind of technology nanocrystal is provided.
The synthetic method of water-soluble monodispersed spherical silver nanocrystal of the present invention may further comprise the steps:
(1) use high purity water with needed raw material natrium citricum, auxiliary additive and soluble silver salt be mixed with respectively mass percent concentration be 1% sodium citrate solution, concentration be 0.1 mM/liter-100 mMs/liter auxiliary additive solution and mass percent concentration be 1% silver soluble salting liquid; Auxiliary additive is meant and can generates sedimentary material (like copper bromide, KI, sodium chloride, sodium sulphate, sodium phosphate, sodium carbonate or vulcanized sodium etc.) with silver ion; Soluble silver salt is meant silver nitrate or silver perchlorate;
(2) by volume the ratio of 5-20:100:3-5:25 take by weighing respectively concentration be 100 mMs/liter sodium citrate solution, auxiliary additive solution and the silver soluble salting liquid of vitamin c solution and step (1) preparation;
(3) vitamin c solution is added just in the boiling water of ebuillition of heated;
(4) sodium citrate solution, auxiliary additive solution and the mixing of silver soluble salting liquid after 3-6 minute, are added rapidly and contain in the ascorbic boiling water;
(5) keep boiling, reflux was cooled to room temperature after 1 hour, can obtain monodispersed spherical silver nanocrystal.
The present invention adopts the auxiliary natrium citricum reduction soluble silver salt of additive to prepare monodispersed spherical silver nanocrystal; Compare other synthetic method; This method is simple to operate, can obtain high-quality, water-soluble monodispersed spherical silver nanocrystal that other existing method can't obtain.
Description of drawings
Fig. 1 is the transmission electron microscope photo of the monodispersed spherical silver nanocrystal of embodiment 1 gained.
The specific embodiment
Embodiment 1
After at first used glassware (there-necked flask and 10 milliliters vial) being put into chloroazotic acid and is soaked 2 hours, with sodium nitrate saturated solution and high purity water cleaning, dry for standby.Use high purity water that needed raw material natrium citricum, silver nitrate and copper bromide are configured to solution respectively, wherein the mass percent concentration of sodium citrate solution is 1%, and the mass percent concentration of liquor argenti nitratis ophthalmicus is 1%, the concentration of copper bromide solution be 4 mMs/liter.There-necked flask is fixed on the warm table and adds 47.5 milliliters high purity water, be heated to boiling rapidly.The vitamin C of 50 microlitres (100 mMs/liter) is added in the boiling water.After then 1 milliliter of sodium citrate solution, 50 microlitre copper bromides and 250 microlitre liquor argenti nitratis ophthalmicuses being mixed 3 minutes, add rapidly and contain in the ascorbic boiling water.Keep boiling at last, reflux was cooled to room temperature after 1 hour, can obtain monodispersed spherical silver nanocrystal, and the transmission electron microscope photo of spherical silver nanocrystal is as shown in Figure 1.
Embodiment 2
The difference one of present embodiment and embodiment be the concentration of copper bromide solution be 10 mMs/liter; The 2nd, the vitamin C of 75 microlitres (100 mMs/liter) is added in the boiling water; All the other conditions are all identical with embodiment 1, can obtain monodispersed spherical silver nanocrystal equally.
Embodiment 3
The difference one of present embodiment and embodiment be the concentration of copper bromide solution be 10 mMs/liter; The 2nd, the vitamin C of 100 microlitres (100 mMs/liter) is added in the boiling water; All the other conditions are all identical with embodiment 1, can obtain monodispersed spherical silver nanocrystal equally.
Embodiment 4
After at first used glassware (there-necked flask and 10 milliliters vial) being put into chloroazotic acid and is soaked 2 hours, with sodium nitrate saturated solution and high purity water cleaning, dry for standby.Use high purity water that needed raw material natrium citricum, silver nitrate and KI are made into sodium citrate solution, liquor argenti nitratis ophthalmicus and liquor kalii iodide; Wherein the mass percent concentration of sodium citrate solution is 1%; The mass percent concentration of liquor argenti nitratis ophthalmicus is 1%, the concentration of liquor kalii iodide be 0.1 mM/liter.Then the vitamin C of 50 microlitres (100 mMs/liter) is added in the boiling water.After then 1 milliliter of sodium citrate solution, 30 microlitre liquor kalii iodides and 250 microlitre liquor argenti nitratis ophthalmicuses being mixed 5 minutes, add rapidly and contain in the ascorbic boiling water.Keep boiling at last, reflux was cooled to room temperature after 1 hour, can obtain monodispersed spherical silver nanocrystal.
Embodiment 5
The difference of present embodiment and embodiment is that the vitamin C of 75 microlitres (100 mMs/liter) is added in the boiling water, and all the other conditions are all identical with embodiment 4, can obtain monodispersed spherical silver nanocrystal equally.
Embodiment 6
The difference of present embodiment and embodiment is that the vitamin C of 100 microlitres (100 mMs/liter) is added in the boiling water, and all the other conditions are all identical with embodiment 4, can obtain monodispersed spherical silver nanocrystal equally.
Embodiment 7
After at first used glassware (there-necked flask and 10 milliliters vial) being put into chloroazotic acid and is soaked 2 hours, with sodium nitrate saturated solution and high purity water cleaning, dry for standby.Use high purity water that needed raw material natrium citricum, silver nitrate and sodium chloride are made into sodium citrate solution, liquor argenti nitratis ophthalmicus and sodium chloride solution; Wherein the mass percent concentration of sodium citrate solution is 1%; The mass percent concentration of liquor argenti nitratis ophthalmicus is 1%, the concentration of sodium chloride solution be 100 mMs/liter.Vitamin C with 50 microlitres adds in the boiling water then.After then 1 milliliter of sodium citrate solution, 40 microlitre sodium chloride solutions and 250 microlitre liquor argenti nitratis ophthalmicuses being mixed 6 minutes, add rapidly and contain in the ascorbic boiling water.Keep boiling at last, reflux was cooled to room temperature after 1 hour, can obtain monodispersed spherical silver nanocrystal.
Embodiment 8
The difference of present embodiment and embodiment is that the vitamin C of 100 microlitres (100 mMs/liter) is added in the boiling water, and all the other conditions are all identical with embodiment 7, can obtain monodispersed spherical silver nanocrystal equally.
Embodiment 9
The difference of present embodiment and embodiment is that the vitamin C of 200 microlitres (100 mMs/liter) is added in the boiling water, and all the other conditions are all identical with embodiment 7, can obtain monodispersed spherical silver nanocrystal equally.
Embodiment 10
After at first used glassware (there-necked flask and 10 milliliters vial) being put into chloroazotic acid and is soaked 2 hours, with sodium nitrate saturated solution and high purity water cleaning, dry for standby.Use high purity water that needed raw material natrium citricum, silver nitrate and vulcanized sodium are made into sodium citrate solution, liquor argenti nitratis ophthalmicus and sodium sulfide solution; Wherein the mass percent concentration of sodium citrate solution is 1%; The mass percent concentration of liquor argenti nitratis ophthalmicus is 1%, the concentration of sodium sulfide solution be 0.1 mM/liter.Vitamin C with 50 microlitres adds in the boiling water then.After then 1 milliliter of sodium citrate solution, 30 microlitre sodium sulfide solutions and 250 microlitre liquor argenti nitratis ophthalmicuses being mixed 4 minutes, add rapidly and contain in the ascorbic boiling water.Keep boiling at last, reflux was cooled to room temperature after 1 hour, can obtain monodispersed spherical silver nanocrystal.
Embodiment 11
After at first used glassware (there-necked flask and 10 milliliters vial) being put into chloroazotic acid and is soaked 2 hours, with sodium nitrate saturated solution and high purity water cleaning, dry for standby.Use high purity water that needed raw material natrium citricum, silver perchlorate and sodium sulphate are made into sodium citrate solution, liquor argenti nitratis ophthalmicus and metabisulfite solution; Wherein the mass percent concentration of sodium citrate solution is 1%; The mass percent concentration of silver perchlorate solution is 1%, the concentration of metabisulfite solution be 80 mMs/liter.Vitamin C with 50 microlitres adds in the boiling water then.After then 1 milliliter of sodium citrate solution, 30 microlitre metabisulfite solutions and 250 microlitre liquor argenti nitratis ophthalmicuses being mixed 5 minutes, add rapidly and contain in the ascorbic boiling water.Keep boiling at last, reflux was cooled to room temperature after 1 hour, can obtain monodispersed spherical silver nanocrystal.
Embodiment 12
After at first used glassware (there-necked flask and 10 milliliters vial) being put into chloroazotic acid and is soaked 2 hours, with sodium nitrate saturated solution and high purity water cleaning, dry for standby.Use high purity water that needed raw material natrium citricum, silver nitrate and sodium carbonate are made into sodium citrate solution, liquor argenti nitratis ophthalmicus and sodium carbonate liquor; Wherein the mass percent concentration of sodium citrate solution is 1%; The mass percent concentration of liquor argenti nitratis ophthalmicus is 1%, the concentration of sodium carbonate liquor be 0.1 mM/liter.Vitamin C with 50 microlitres adds in the boiling water then.After then 1 milliliter of sodium citrate solution, 100 microlitre sodium carbonate liquors and 250 microlitre liquor argenti nitratis ophthalmicuses being mixed 5 minutes, add rapidly and contain in the ascorbic boiling water.Keep boiling at last, reflux was cooled to room temperature after 1 hour, can obtain monodispersed spherical silver nanocrystal.
Embodiment 13
After at first used glassware (there-necked flask and 10 milliliters vial) being put into chloroazotic acid and is soaked 2 hours, with sodium nitrate saturated solution and high purity water cleaning, dry for standby.Use high purity water that needed raw material natrium citricum, silver perchlorate and sodium phosphate are made into sodium citrate solution, silver perchlorate solution and sodium radio-phosphate,P-32 solution; Wherein the mass percent concentration of sodium citrate solution is 1%; The mass percent concentration of silver perchlorate solution is 1%, the concentration of sodium radio-phosphate,P-32 solution be 0.1 mM/liter.Vitamin C with 50 microlitres adds in the boiling water then.After then 1 milliliter of sodium citrate solution, 100 microlitre sodium radio-phosphate,P-32 solutions and 250 microlitre liquor argenti nitratis ophthalmicuses being mixed 5 minutes, add rapidly and contain in the ascorbic boiling water.Keep boiling at last, reflux was cooled to room temperature after 1 hour, can obtain monodispersed spherical silver nanocrystal.
Claims (1)
1. the synthetic method of a water-soluble monodispersed spherical silver nanocrystal is characterized in that, may further comprise the steps:
(1) use high purity water with needed raw material natrium citricum, auxiliary additive and soluble silver salt be mixed with respectively mass percent concentration be 1% sodium citrate solution, concentration be 0.1 mM/liter-100 mMs/liter auxiliary additive solution and mass percent concentration be 1% silver soluble salting liquid; Auxiliary additive is meant and can generates sedimentary material with silver ion; Soluble silver salt is meant silver nitrate or silver perchlorate;
(2) by volume the ratio of 5-20:100:3-5:25 take by weighing respectively concentration be 100 mMs/liter sodium citrate solution, auxiliary additive solution and the silver soluble salting liquid of vitamin c solution and step (1) preparation;
(3) vitamin c solution is added just in the boiling water of ebuillition of heated;
(4) sodium citrate solution, auxiliary additive solution and the mixing of silver soluble salting liquid after 3-6 minute, are added rapidly and contain in the ascorbic boiling water;
(5) keep boiling, reflux was cooled to room temperature after 1 hour, can obtain monodispersed spherical silver nanocrystal.
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Cited By (4)
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| CN105252019A (en) * | 2015-11-20 | 2016-01-20 | 济南大学 | Preparation method of highly-dispersed spherical nano-silver |
| CN105965029A (en) * | 2016-06-02 | 2016-09-28 | 山东大学 | Method for synthesizing water-soluble monodisperse spherical-like gold-silver alloy nano-particles |
| CN109663929A (en) * | 2019-01-24 | 2019-04-23 | 兰州石化职业技术学院 | A kind of preparation method of rule nanogold particle |
| CN114260461A (en) * | 2021-12-28 | 2022-04-01 | 成都市天甫金属粉体有限责任公司 | Multi-fold spherical silver powder and preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105965029A (en) * | 2016-06-02 | 2016-09-28 | 山东大学 | Method for synthesizing water-soluble monodisperse spherical-like gold-silver alloy nano-particles |
| CN105965029B (en) * | 2016-06-02 | 2017-12-01 | 山东大学 | The synthetic method of water-soluble monodispersed spherical gold-silver alloy nano particle |
| CN109663929A (en) * | 2019-01-24 | 2019-04-23 | 兰州石化职业技术学院 | A kind of preparation method of rule nanogold particle |
| CN109663929B (en) * | 2019-01-24 | 2021-07-23 | 兰州石化职业技术学院 | Preparation method of regular nano gold particles |
| CN114260461A (en) * | 2021-12-28 | 2022-04-01 | 成都市天甫金属粉体有限责任公司 | Multi-fold spherical silver powder and preparation method and application thereof |
| CN114260461B (en) * | 2021-12-28 | 2023-11-03 | 成都市天甫金属粉体有限责任公司 | Multi-fold spherical silver powder and preparation method and application thereof |
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