CN107552810B - Preparation method of nano silver cubic particles - Google Patents
Preparation method of nano silver cubic particles Download PDFInfo
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- CN107552810B CN107552810B CN201710826441.0A CN201710826441A CN107552810B CN 107552810 B CN107552810 B CN 107552810B CN 201710826441 A CN201710826441 A CN 201710826441A CN 107552810 B CN107552810 B CN 107552810B
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Abstract
The invention relates to a preparation method of nano silver cubic particles, which comprises the steps of dispersing silver salt in polyhydric alcohol to obtain silver salt dispersion liquid; dispersing polyvinylpyrrolidone in polyol to obtain polyvinylpyrrolidone dispersion liquid; dispersing hydrochloric acid in polyol to obtain hydrochloric acid dispersion liquid; and mixing the obtained silver nitrate dispersion liquid, polyvinylpyrrolidone dispersion liquid and hydrochloric acid dispersion liquid, reacting, and carrying out solid-liquid separation on the product to obtain the nano silver cubic particles. The preparation method has the advantages of simple process, high yield, simple reaction system, easy control and capability of stably and reliably obtaining the high-purity nano silver cubic particles.
Description
Technical Field
The invention belongs to the field of metal nano materials, and relates to a preparation method of nano silver cubic particles.
Background
The silver nanomaterial is one of nanomaterials. Among various metal nano materials, silver nano materials have the advantages of good electronic property, optical property, mechanical property and catalytic property, good antibacterial property, biocompatibility, easy surface modification and the like, and become hot spots of research of scientists all over the world. In industry, silver nano material is a very important nano material, and has wide application in the fields of biomedicine, chemical catalysis, ceramic materials, sewage treatment, coatings and high-performance electrode materials. Particularly, the silver nanocube material is one of silver nanomaterials, has very remarkable optical signal enhancement characteristics, catalytic characteristics and the like compared with silver nanomaterials with other morphologies, is widely used as a surface plasma enhancement material and a Raman enhancement material, and is a hotspot of research in recent years.
One key obstacle to the large scale application of silver nanomaterials is that they are difficult to synthesize stably. The preparation methods of the nano-materials are various, and mainly include chemical methods, physical methods, biological reduction methods and the like. The chemical reduction method has the characteristics of simple operation, stable and controllable reaction, uniform particle size distribution and the like, and is widely used for preparing nano silver materials. The method generally comprises the step of reducing metal ions into metal simple substances by using a reducing agent in a solvent system in the atmosphere of a surfactant. In the synthesis of nano silver particles, the polyol method is also the main synthesis method. The main problems encountered in the current preparation of nano-silver particles are the stability and reaction yield of the preparation process, and the preparation scale of the current nano-silver particles is mostly in milligram level, and the stability cannot be guaranteed.
CN104889418A discloses a biosynthesis method of cubic nano silver particles, which takes sweet orange peel extract and lotus leaf extract as reducing agent and protective agent, takes silver nitrate as silver source, adjusts the mixed solution to a proper pH environment, and reacts at 60 ℃ to obtain the nano silver particles with a more regular cubic shape.
CN106001607A discloses a method for preparing nano silver cubes in a hydrophobic phase, which takes oleylamine as a solvent, silver bromide as a silver source and triphenylphosphine as a stabilizer to react for 2 hours at 250 ℃ to obtain a nano silver cube product.
Disclosure of Invention
In order to solve the problems of the existing nano silver particle synthesis technology, the invention provides a preparation method of nano silver cubic particles, which has the advantages of simple process, high yield, simple reaction system, easy control and capability of stably and reliably obtaining high-purity nano silver cubic particles.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of nano silver cubic particles, which comprises the following steps:
(1) dispersing silver salt in polyhydric alcohol to obtain silver salt dispersion liquid; dispersing polyvinylpyrrolidone in polyol to obtain polyvinylpyrrolidone dispersion liquid; dispersing hydrochloric acid in polyol to obtain hydrochloric acid dispersion liquid;
(2) and (2) mixing the silver salt dispersion liquid, the polyvinylpyrrolidone dispersion liquid and the hydrochloric acid dispersion liquid obtained in the step (1), reacting under the condition that silver ions can be reduced into metallic silver, and carrying out solid-liquid separation to obtain the nano silver cubic particles.
In a preferred embodiment of the present invention, the polyhydric alcohol used in each dispersion in step (1) is independently any one or any combination of at least two of ethylene glycol, diethylene glycol, glycerol, 1, 2-propanediol, or pentaerythritol, preferably ethylene glycol.
As a preferred technical solution of the present invention, the silver salt in step (1) is any one or a combination of at least two of silver acetate, silver bromide, silver nitrate and silver chloride, preferably silver nitrate.
In a preferred embodiment of the present invention, the concentration of silver in the silver dispersion in step (1) is 85 to 110mM, preferably 90 mM.
As a preferred technical solution of the present invention, the polyvinylpyrrolidone in step (1) includes any one or a combination of at least two of PVPK12, PVPK15, PVPK30, PVPK45, PVPK60 or PVPK-70, preferably PVPK 30; preferably, the concentration of the polyvinylpyrrolidone in the polyvinylpyrrolidone dispersion liquid in the step (1) is 90-180 mM, and preferably 120-150 mM.
In a preferred embodiment of the present invention, the concentration of hydrogen chloride in the hydrochloric acid dispersion in step (1) is 1 to 30mM, preferably 8 to 18 mM.
In a preferred embodiment of the present invention, the molar ratio of silver, polyvinylpyrrolidone and hydrochloric acid in the mixing in step (2) is 30 to 45% silver: 50% -64% of polyvinylpyrrolidone: 0.1 to 0.9 percent of hydrochloric acid.
As a preferable technical scheme of the invention, the reaction in the step (2) is carried out under stirring, and the rotation speed of the stirring is 400-1500 r/min, preferably 600-1200 r/min, preferably 700-1000 r/min; for example, 650r/min, 800r/min, 1100r/min or 1300r/min, etc., but is not limited to the recited values, and other values not recited within the numerical range are equally applicable;
preferably, the temperature of the reaction in step (2) is 120 to 180 ℃, preferably 130 to 160 ℃, more preferably 140 to 160 ℃, for example 120 ℃, 140 ℃, 150 ℃ or 160 ℃, etc., but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the reaction time in step (2) is 12 to 36 hours, preferably 10 to 24 hours, more preferably 14 to 20 hours, such as 12 hours, 15 hours, 18 hours or 20 hours, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferred technical scheme of the invention, the solid-liquid separation method in the step (2) comprises any one or a combination of at least two of filtration, sedimentation, evaporation or centrifugation, and is preferably centrifugation.
As a preferred embodiment of the present invention, the preparation method further comprises:
(3) washing and drying the nano silver cubic particles obtained after the solid-liquid separation in the step (2);
preferably, the washing solution used in the washing in step (3) is deionized water, any one or a combination of any two of anhydrous ethanol and acetone, and is preferably deionized water.
Preferably, the drying method in step (3) is vacuum drying or normal pressure drying, preferably vacuum drying.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) dispersing silver salt in polyhydric alcohol to obtain silver salt dispersion liquid with the concentration of 85-110 mM, dispersing polyvinylpyrrolidone in the polyhydric alcohol to obtain polyvinylpyrrolidone dispersion liquid with the concentration of 90-180 mM, preferably 120-150 mM, and dispersing hydrochloric acid in the polyhydric alcohol to obtain hydrochloric acid dispersion liquid with the concentration of 1-30 mM, preferably 8-18 mM;
(2) and (2) mixing the silver salt dispersion liquid obtained in the step (1), polyvinylpyrrolidone and hydrochloric acid dispersion liquid, reacting for 15-36h at the rotating speed of 400-1500 r/min and the temperature of 120-160 ℃, and carrying out solid-liquid separation, washing and drying to obtain the nano silver cubic particles.
The nano silver cubic particles obtained by the preparation method provided by the invention have a cubic crystal structure, the average size of the nano silver cubic particles is usually more than 40nm, such as 80nm, and less than 400nm, such as 220nm, the standard deviation is within 10nm, and the purity is at least 70%, such as at least 85%.
The nano silver cubic particles obtained by the preparation method provided by the invention are suitable for various applications, such as the fields of catalytic materials, optical characterization and the like.
Compared with the prior art, the preparation method of the invention at least has the following beneficial effects:
(1) the invention provides a preparation method of nano silver cubic particles, and raw materials used in the method are basically nontoxic and pollution-free, the reaction is simple and easy to operate, the working procedure is simple, no special reaction condition requirements exist, and the equipment requirements are low.
(2) The invention provides a preparation method of nano silver cubic particles, which is a one-step reaction, the reaction process is stable and easy to control, the purity of a final product is high, and a complex purification process is not needed.
(3) The invention provides a preparation method of nano silver cubic particles, and the method has the advantages that under the optimized condition, the size of a final product is controllable, and different requirements can be met.
(4) The invention provides a preparation method of nano silver cubic particles, which has high one-time reaction yield and can meet the requirements of conventional application.
Detailed Description
For the convenience of understanding the present invention, the following examples are listed. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A preparation method of nano silver cubic particles comprises the following steps:
(1) dispersing 0.85mmol of silver nitrate into 10m L of ethylene glycol to obtain a silver nitrate dispersion, dispersing 0.96mmol of PVPK30 into 10ml of ethylene glycol to obtain a polyvinylpyrrolidone dispersion, and dispersing 0.003mmol of hydrochloric acid into 3ml of ethylene glycol to obtain a hydrochloric acid dispersion;
(2) mixing the silver nitrate dispersion liquid, the polyvinylpyrrolidone dispersion liquid and the hydrochloric acid dispersion liquid obtained in the step (1), reacting for 20 hours at 140 ℃ under the stirring of 800r/min, and performing centrifugal separation to obtain initial nano silver cubic particles;
(3) and (3) taking deionized water as a solvent, centrifugally washing the nano-silver cubic particles obtained in the step (2) at the rotating speed of 3000rpm, dropping the nano-silver cubic particles to the bottom of a centrifugal tube, discarding supernatant to finish one washing operation, repeating the washing operation for three times, collecting obtained precipitates, and placing the precipitates in a vacuum oven to dry at normal temperature for 2 hours to obtain the final nano-silver cubic particles.
Example 2
A preparation method of nano silver cubic particles comprises the following steps:
(1) dispersing 1.1mmol of silver nitrate in 10m L of ethylene glycol to obtain a silver nitrate dispersion, dispersing 1.3mmol of PVPK30 in 10ml of ethylene glycol to obtain a polyvinylpyrrolidone dispersion, and dispersing 0.018mmol of hydrochloric acid in 3ml of ethylene glycol to obtain a hydrochloric acid dispersion;
(2) mixing the silver nitrate dispersion liquid obtained in the step (1), the polyvinylpyrrolidone dispersion liquid and the hydrochloric acid dispersion liquid, reacting for 20 hours at 140 ℃ under the stirring of 800r/min, and performing centrifugal separation to obtain initial nano silver cubic particles;
(3) and (3) taking deionized water as a solvent, centrifugally washing the nano-silver cubic particles obtained in the step (2) at the rotating speed of 3000rpm, dropping the nano-silver cubic particles to the bottom of a centrifugal tube, discarding supernatant to finish one washing operation, repeating the washing operation for three times, collecting obtained precipitates, and placing the precipitates in a vacuum oven to dry at normal temperature for 2 hours to obtain the final nano-silver cubic particles.
Example 3
A preparation method of nano silver cubic particles comprises the following steps:
(1) dispersing 0.85mmol of silver nitrate in 10m L of diethylene glycol to obtain a silver nitrate dispersion, dispersing 0.96mmol of PVPK70 in 10ml of diethylene glycol to obtain a polyvinylpyrrolidone dispersion, and dispersing 0.003mmol of hydrochloric acid in 3ml of diethylene glycol to obtain a hydrochloric acid dispersion;
(2) mixing the silver nitrate dispersion liquid obtained in the step (1), the polyvinylpyrrolidone dispersion liquid and the hydrochloric acid dispersion liquid, reacting for 20 hours at 140 ℃ under the stirring of 800r/min, and performing centrifugal separation to obtain initial nano silver cubic particles;
(3) and (3) taking deionized water as a solvent, centrifugally washing the nano-silver cubic particles obtained in the step (2) at the rotating speed of 3000rpm, dropping the nano-silver cubic particles to the bottom of a centrifugal tube, discarding supernatant to finish one washing operation, repeating the washing operation for three times, collecting obtained precipitates, and placing the precipitates in a vacuum oven to dry at normal temperature for 2 hours to obtain the final nano-silver cubic particles.
Example 4
A preparation method of nano silver cubic particles comprises the following steps:
(1) dispersing 0.85mmol of silver nitrate into 10m L of ethylene glycol to obtain a silver nitrate dispersion, dispersing 0.96mmol of PVPK45 into 10ml of ethylene glycol to obtain a polyvinylpyrrolidone dispersion, and dispersing 0.003mmol of hydrochloric acid into 3ml of ethylene glycol to obtain a hydrochloric acid dispersion;
(2) mixing the silver nitrate dispersion liquid obtained in the step (1), the polyvinylpyrrolidone dispersion liquid and the hydrochloric acid dispersion liquid, reacting for 24 hours at the temperature of 150 ℃ under the stirring of 1500r/min, and performing centrifugal separation to obtain initial nano silver cubic particles;
(3) and (3) taking deionized water as a solvent, centrifugally washing the nano-silver cubic particles obtained in the step (2) at the rotating speed of 3000rpm, dropping the nano-silver cubic particles to the bottom of a centrifugal tube, discarding supernatant to finish one washing operation, repeating the washing operation for three times, collecting obtained precipitates, and placing the precipitates in a vacuum oven to dry at normal temperature for 2 hours to obtain the final nano-silver cubic particles.
Example 5
A method for preparing nano silver cubic particles, the method comprising the steps of:
(1) dispersing 0.85mmol of silver acetate in 10m L glycerol to obtain a silver acetate dispersion, dispersing 0.96mmol of PVPK15(5500) in 10ml glycerol to obtain a polyvinylpyrrolidone dispersion, and dispersing 0.003mmol of hydrochloric acid in 3ml glycerol to obtain a hydrochloric acid dispersion;
(2) mixing the silver nitrate dispersion liquid obtained in the step (1), the polyvinylpyrrolidone dispersion liquid and the hydrochloric acid dispersion liquid, reacting for 36 hours at 120 ℃ under the stirring of 1000r/min, and performing centrifugal separation to obtain initial nano silver cubic particles;
(3) and (3) taking deionized water as a solvent, centrifugally washing the nano-silver cubic particles obtained in the step (2) at the rotating speed of 3000rpm, dropping the nano-silver cubic particles to the bottom of a centrifugal tube, discarding supernatant to finish one washing operation, repeating the washing operation for three times, collecting obtained precipitates, and placing the precipitates in a vacuum oven to dry at normal temperature for 2 hours to obtain the final nano-silver cubic particles.
The nano silver cubic particles prepared in examples 1 to 5 were tested for average size and purity, and size distribution and purity were tested by Scanning Electron Microscope (SEM) and laser particle size tester in a conventional manner in the art. The results are shown in Table 1.
TABLE 1
| Item | Size of | Purity of | Yield of |
| Example 1 | 135±7nm | 91％ | 95％ |
| Example 2 | 153±10nm | 83％ | 89％ |
| Example 3 | 148±9nm | 85％ | 91％ |
| Example 4 | 175±12nm | 81％ | 85％ |
| Example 5 | 240±13nm | 79％ | 82％ |
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (6)
1. A method for preparing nano silver cubes is characterized by comprising the following steps:
dispersing silver salt in polyhydric alcohol to obtain silver salt dispersion liquid; dispersing polyvinylpyrrolidone in polyol to obtain polyvinylpyrrolidone dispersion liquid; dispersing hydrochloric acid in polyol to obtain hydrochloric acid dispersion liquid; wherein the polyalcohol is selected from any one or any combination of at least two of ethylene glycol, diethylene glycol, glycerol, 1, 2-propylene glycol or pentaerythritol; the concentration of silver in the silver salt dispersion liquid is 85-110 mM; the concentration of hydrogen chloride in the hydrochloric acid dispersion liquid is 8-18 mM;
mixing the silver salt dispersion liquid, the polyvinylpyrrolidone dispersion liquid and the hydrochloric acid dispersion liquid, reacting under the condition that silver ions can be reduced to metallic silver, and carrying out solid-liquid separation to obtain nano silver cubic particles, wherein the reaction is carried out under stirring, the rotating speed of stirring is 400-1500 r/min, the temperature of the reaction is 120-180 ℃, and the time of the reaction is 12-36 hours; wherein in the step of mixing the silver salt dispersion liquid, the polyvinylpyrrolidone dispersion liquid and the hydrochloric acid dispersion liquid, the molar ratio of silver to polyvinylpyrrolidone to hydrochloric acid is 30-45% silver: 50% -64% of polyvinylpyrrolidone: 0.1 to 0.9 percent of hydrochloric acid;
the prepared nano silver cubic particles have a cubic crystal structure, the average size is 135 nm-240 nm, and the purity is at least 85%.
2. The method according to claim 1, wherein the silver salt is any one of silver acetate, silver bromide, silver nitrate or silver chloride or a combination of at least two of them.
3. The method of claim 1, wherein the polyvinylpyrrolidone comprises any one of or a combination of at least two of PVPK12, PVPK15, PVPK30, PVPK45, PVPK60 or PVPK 70.
4. The method according to any one of claims 1 to 3, wherein in the step of reacting under conditions that allow reduction of silver ions to metallic silver, the stirring is performed at a rotation speed of 600 to 1200 r/min; the reaction temperature is 130-160 ℃; the reaction time is 10-24 h.
5. The method according to any one of claims 1 to 3, wherein the solid-liquid separation means comprises any one or a combination of at least two of filtration, sedimentation, evaporation or centrifugation.
6. The production method according to any one of claims 1 to 3, characterized by further comprising: and washing and drying the nano silver cubic particles obtained after solid-liquid separation.
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| CN108732221A (en) * | 2018-04-12 | 2018-11-02 | 南京工业大学 | A kind of preparation method of electrode print slurry |
| CN110181071A (en) * | 2019-05-14 | 2019-08-30 | 深圳先进技术研究院 | Nano-Ag particles and its preparation method and application |
| CN113600828B (en) * | 2021-08-19 | 2022-10-11 | 南京工业大学 | Protection method of silver nanoparticles |
| CN113953524A (en) * | 2021-10-12 | 2022-01-21 | 浙江工业大学 | Novel synthesis of nano-silver colloid by polyol solvothermal method |
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| CN1552547A (en) * | 2003-06-05 | 2004-12-08 | 中国科学院理化技术研究所 | Preparing method for cubic silver nanometer grain |
| CN103658678A (en) * | 2014-01-06 | 2014-03-26 | 景德镇陶瓷学院 | Preparation method for silver nanocubes |
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| JP5104211B2 (en) * | 2007-10-26 | 2012-12-19 | 住友金属鉱山株式会社 | Silver powder manufacturing method |
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| CN102744417B (en) * | 2011-06-16 | 2016-03-30 | 浙江科创新材料科技有限公司 | A kind of preparation method of nano silver wires with high length-diameter ratio |
| CN103100724B (en) * | 2013-02-21 | 2015-04-08 | 中国科学院深圳先进技术研究院 | Preparation method of silver nanowires |
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| CN1552547A (en) * | 2003-06-05 | 2004-12-08 | 中国科学院理化技术研究所 | Preparing method for cubic silver nanometer grain |
| CN103658678A (en) * | 2014-01-06 | 2014-03-26 | 景德镇陶瓷学院 | Preparation method for silver nanocubes |
| CN104985191A (en) * | 2015-07-08 | 2015-10-21 | Tcl集团股份有限公司 | Silver nano cube with monodispersity and preparation method and conductive ink thereof |
| CN106964785A (en) * | 2017-04-20 | 2017-07-21 | 中国科学院深圳先进技术研究院 | A kind of preparation method of nano-Ag particles |
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