CN100563881C - A kind of method of polyacrylic acid hydro-thermal synthesis of nano gold - Google Patents
A kind of method of polyacrylic acid hydro-thermal synthesis of nano gold Download PDFInfo
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- CN100563881C CN100563881C CNB2008100705219A CN200810070521A CN100563881C CN 100563881 C CN100563881 C CN 100563881C CN B2008100705219 A CNB2008100705219 A CN B2008100705219A CN 200810070521 A CN200810070521 A CN 200810070521A CN 100563881 C CN100563881 C CN 100563881C
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Abstract
A kind of method of polyacrylic acid hydro-thermal synthesis of nano gold relates to a kind of nm of gold.Provide that a kind of operating procedure is simple, raw material obtains easily, with low cost, be applicable to large-scale industrial production; also the change of condition obtains the gold nano grain or the gold-nano-piece of different sizes and shape by experiment; the production process environmentally safe meets the method for the polyacrylic acid hydro-thermal synthesis of nano gold that " Green Chemistry " advocated require.In water, add polymer, stirring and dissolving; Treat that polymer dissolves the back fully and adds gold chloride, stir, get the reaction precursor liquid solution; Pour the reaction precursor liquid solution into polytetrafluoroethyllining lining, and in the autoclave of packing into, the sealing afterreaction; Reaction system is cooled to room temperature, and the centrifugal golden nanometer particle that is synthesized that makes separates with polymer, cleans with ethanol then, promptly gets nm of gold.The gained nm of gold generally comprises gold nano grain or/and gold-nano-piece.
Description
Technical field
The present invention relates to a kind of nm of gold, especially relate to a kind of method of utilizing synthetic golden nanometer particle of polyacrylic acid hydro-thermal method and gold-nano-piece.
Background technology
Because nm of gold has skin effect, small-size effect and macro quanta tunnel effect etc., makes it have the many peculiar properties that are different from the body gold, as optical property, catalytic property and chemical reactivity etc., has wide practical use in a lot of fields.The preparation method of nm of gold mainly contains at present: oxidation-reduction method, photochemical method, template, the golden growth method of kind and electrochemical reducing etc.Polyacrylic acid (PAA) is the important water-soluble polymer of a class, and the physics and the chemical property of many excellences arranged: 1) viscosity is big; 2) good heat resistance; 3) hydrability is strong; 4) can seal trace metal ion; 5) good mechanical stability; 6) strong to protein adherence power; 7) the emulsification dispersion stabilization is good.Because polyacrylic these characteristics all are widely used it in industry such as coating, papermaking, weaving, oil recovery, mining, metallurgy, food, medicine, cosmetics, civil engineering and water treatment.Discover that polyacrylic acid not only has reproducibility, and the functional group on the chain can also interact with metal ion, can be used as the coating agent of metal ion.Therefore, polyacrylic acid also is used to prepare noble metal.Boris G..Ershov (referring to document: Boris G..Ershov, Arnim Henglein, J.Phys.Chem.B, 1998,102,10663-10666) adopt polyacrylic acid and Sodium Polyacrylate, under radiation gamma, reduce AgNO
3Huber (referring to document: Klaus Huber, Thomas Witte, Jutta Hollman, SusanneKeuker-Baumann, J.AM.CHEM.SOC, 2007,129,1089-1094) adopt photochemical method, under ultra violet lamp, utilize Sodium Polyacrylate with Ag
+Be reduced into silver nano-grain.But the size and the shape of the metal nanoparticle that obtains with these methods are all wayward, and the particle diameter wider distribution.
Hydro-thermal is synthetic to be the emerging in recent years method for preparing nano particle.Hydro-thermal method has another name called hydrothermal method, be meant in sealed pressure vessel, be solvent with water, high temperature (＞100 ℃), high pressure (under＞9.81Mpa) the condition, the method for research, rapidoprint.Hydro-thermal method is to carry out basic research in the geology field the earliest, turns to the research of functional material in 1905 later on.Adopt the Hydrothermal Preparation nano material then just grew up in recent years (referring to patent: the method for hydrothermally synthesizing series flower shape zinc oxide micrometer/nanometer structure, application number: 200610117564.9, publication number: 1944708A).Compare with other preparation methods, the Hydrothermal Preparation technology has following characteristics: 1) be reflected under the HTHP and carry out, reaction speed is very fast and might be implemented in the reaction that can not carry out under the normal condition; 2) change hydro-thermal reaction environment (pH value, raw material proportioning etc.), can obtain the nano particle of different structure and shape; 3), can obtain the product of different-grain diameter by control hydrothermal reaction condition (predecessor form, reaction temperature, reaction time etc.).The nano particle purity height that hydro-thermal method makes, narrow diameter distribution, good dispersion, the reunion degree is low, crystal formation good, composition is pure, and since the hydrothermal preparation process pollute little, cost is low, be applicable to industrialization production, its development prospect is wide.
Summary of the invention
The object of the present invention is to provide that a kind of operating procedure is simple, raw material obtains easily, with low cost, be applicable to large-scale industrial production; also the change of condition obtains the gold nano grain or the gold-nano-piece of different sizes and shape by experiment; the production process environmentally safe meets the method for the polyacrylic acid hydro-thermal synthesis of nano gold that " Green Chemistry " advocated require.
Technical scheme of the present invention is to be reducing agent and coating agent with the polyacrylic acid, adopts hydro-thermal method synthesis of nano gold.
The present invention includes following steps:
4) in water, add polymer, stirring and dissolving;
5) treat that polymer dissolves the back fully and adds gold chloride, stir, get the reaction precursor liquid solution;
6) pour the reaction precursor liquid solution into polytetrafluoroethyllining lining, and in the autoclave of packing into, the sealing afterreaction;
4) reaction system is cooled to room temperature, the centrifugal golden nanometer particle that is synthesized that makes separates with polymer, cleans with ethanol then, promptly gets nm of gold.The gained nm of gold generally comprises gold nano grain or/and gold-nano-piece.
Described polymer is a polyacrylic acid or/and Sodium Polyacrylate, and the molecular weight of polymer is 25000～240000, presses mass ratio, Sodium Polyacrylate: polyacrylic acid is preferably 1: (1～10).Gold chloride concentration is preferably 0.01～0.03M.In molar ratio, gold chloride: polymer is preferably 1: (50～500).
The post-reacted temperature of described sealing is preferably 100～200 ℃, and the time of reaction is preferably 40min～4h.
Compare with existing synthetic method, outstanding advantage of the present invention is:
1) polymer of the present invention is a polyacrylic acid or/and Sodium Polyacrylate, low, the easy acquisition of cost of material, good biocompatibility, environmental sound;
2) the present invention can obtain gold nano grain or/and gold-nano-piece by the control to synthesis condition;
3) the present invention utilizes the gold nano grain good dispersion that hydrothermal synthesis method makes, the shape homogeneous, and narrow diameter distribution, the reunion degree is low, good stability;
4) synthetic method craft of the present invention is simple, and the product that obtains is easy to separate, cleans, preserves.
Description of drawings
Fig. 1 is that the ultraviolet-visible of the golden nanometer particle of embodiment 1 preparation absorbs spectrogram.In Fig. 1, abscissa is wavelength (nm), and ordinate is an absorbance; Maximum absorption band is 575nm.
Fig. 2 is the transmission electron microscope picture of the gold-nano-piece of embodiment 2 preparations.In Fig. 2, scale is 200nm.
Fig. 3 is the particle diameter distribution map of the golden nanometer particle of embodiment 3 preparations.In Fig. 3, abscissa is particle diameter (nm), and ordinate is intensity (%); Average grain diameter is 100nm, and polydispersity coefficient is 0.282.
Fig. 4 is the ESEM picture of the gold-nano-piece of embodiment 4 preparations.In Fig. 4, scale is 1 μ m.
Fig. 5 is the ESEM picture of the gold nano grain of embodiment 5 preparations.In Fig. 5, scale is 200nm.
The specific embodiment
Embodiment 1
Get 0.036g polyacrylic acid (molecular weight is 25000), be dissolved in the 27mL water, stir; Add 3mL chlorauric acid solution (0.01M), stir 10min, get the reaction precursor liquid solution; Pour the reaction precursor liquid solution into polytetrafluoroethyllining lining, and in the autoclave of packing into.Sealing is placed on 180 ℃ of baking oven internal reaction 4h; Reaction system is cooled to room temperature.The centrifugal golden nanometer particle that is synthesized that makes separates with polyacrylic acid, cleans three times with ethanol again.The gold nano grain particle diameter that obtains is about 250nm.
Embodiment 2
Get 0.144g Sodium Polyacrylate (molecular weight is 100000), be dissolved in the 28mL water, stir; Add 2mL chlorauric acid solution (0.01M), stir 10min, get the reaction precursor liquid solution; Pour the reaction precursor liquid solution into polytetrafluoroethyllining lining, and in the autoclave of packing into.Sealing is placed on 4h in 140 ℃ of baking ovens; Reaction system is cooled to room temperature.The centrifugal golden nanometer particle that is synthesized that makes separates with Sodium Polyacrylate, cleans three times with ethanol again.The gold nano grain particle diameter that obtains is 150nm, and the gold-nano-piece size that obtains is 400nm, and thickness is 30nm.
Embodiment 3
Get 0.072g polyacrylic acid (molecular weight is 240000), be dissolved in the 29mL water, stir; Add 1mL chlorauric acid solution (0.01M), stir 10min, get the reaction precursor liquid solution; Pour the reaction precursor liquid solution into polytetrafluoroethyllining lining, and in the autoclave of packing into.Sealing is placed on 40min in 200 ℃ of baking ovens; Reaction system is cooled to room temperature.The centrifugal golden nanometer particle that is synthesized that makes separates with polyacrylic acid, cleans three times with ethanol again.The gold nano grain particle diameter that obtains is 100nm.
Embodiment 4
Get 0.108g Sodium Polyacrylate (molecular weight is 50000), be dissolved in the 27mL water, stir; Add 3mL chlorauric acid solution (0.01M), stir 10min, get the reaction precursor liquid solution; Pour the reaction precursor liquid solution into polytetrafluoroethyllining lining, and in the autoclave of packing into.Sealing is placed on 4h in 120 ℃ of baking ovens; Reaction system is cooled to room temperature.The centrifugal golden nanometer particle that is synthesized that makes separates with Sodium Polyacrylate, cleans three times with ethanol again.The gold-nano-piece size that obtains is 1.5 μ m, and thickness is 80nm.
Get 0.18g polyacrylic acid and 0.18g Sodium Polyacrylate respectively, be dissolved in the 29mL water, stir; Add 1mL chlorauric acid solution (0.01M), stir 10min, get the reaction precursor liquid solution; Pour the reaction precursor liquid solution into polytetrafluoroethyllining lining, and in the autoclave of packing into.Sealing is placed on 1h in 120 ℃ of baking ovens; Reaction system is cooled to room temperature.The centrifugal golden nanometer particle that is synthesized that makes separates with polymer, cleans three times with ethanol again.The nanogold particle particle diameter that obtains is 200nm.
Claims (1)
1. the method for a polyacrylic acid hydro-thermal synthesis of nano gold is characterized in that may further comprise the steps:
1) in water, add polymer, stirring and dissolving, the molecular weight of polymer is 25000～240000, described polymer is a polyacrylic acid; Or Sodium Polyacrylate; Or polyacrylic acid and Sodium Polyacrylate, press mass ratio, Sodium Polyacrylate: polyacrylic acid is 1: 1～10;
2) treat that polymer dissolves the back fully and adds gold chloride, stir that get the reaction precursor liquid solution, gold chloride concentration is 0.01～0.03M, in molar ratio, gold chloride: polymer is 1: 50～500;
3) pour the reaction precursor liquid solution into polytetrafluoroethyllining lining, and in the autoclave of packing into, the sealing afterreaction, the temperature of reaction is 100～200 ℃, the time of reaction is 40min～4h;
4) reaction system is cooled to room temperature, the centrifugal golden nanometer particle that is synthesized that makes separates with polymer, cleans with ethanol then, promptly gets nm of gold.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103305881A (en) * | 2013-03-05 | 2013-09-18 | 浙江师范大学 | Porous reticular gold nano-sheet array and preparation method thereof |
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| CN102205421A (en) * | 2010-03-31 | 2011-10-05 | 中国科学院福建物质结构研究所 | Method for preparing gold and silver nanoparticles with hydro-thermal method |
| CN102205420A (en) * | 2010-03-31 | 2011-10-05 | 中国科学院福建物质结构研究所 | Preparation method of water-phase noble metal nano particles |
| CN102266946B (en) * | 2011-07-27 | 2013-02-13 | 厦门大学 | Method for preparing nano-golden particle |
| CN103785854B (en) * | 2014-01-27 | 2016-04-20 | 武汉纺织大学 | A kind of method utilizing sodium alginate green syt nm of gold |
| CN104690265B (en) * | 2015-03-17 | 2017-05-10 | 福州大学 | Golden nanostars and preparation method and application thereof |
| CN104874814A (en) * | 2015-05-15 | 2015-09-02 | 皖南医学院 | Gold hydroxide nano-sphere, porous/hollow gold nano-particle material and preparation methods of gold hydroxide nano-sphere and porous/hollow gold nano-particle material |
| CN108788180A (en) * | 2018-07-06 | 2018-11-13 | 山东大学 | A kind of optical property is controllable and the preparation method of the Ag aggregates of nanoparticles of the reversible assembling of pH response dynamics |
| CN109676153A (en) * | 2019-01-28 | 2019-04-26 | 武汉科技大学 | A kind of method that can prepare simultaneously porous gold nano grain Yu hexagon gold-nano-piece |
| CN109942731B (en) * | 2019-04-08 | 2021-04-27 | 武汉轻工大学 | Preparation method of nanogold/polymethyl methacrylate conductive material |
| CN111208185B (en) * | 2020-02-25 | 2023-01-13 | 杭州电子科技大学 | Preparation method of composite nano material |
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| CN1944708A (en) * | 2006-10-25 | 2007-04-11 | 华东师范大学 | Method for hydrothermally synthesizing series flower shape zinc oxide micron/nano structure |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103305881A (en) * | 2013-03-05 | 2013-09-18 | 浙江师范大学 | Porous reticular gold nano-sheet array and preparation method thereof |
| CN103305881B (en) * | 2013-03-05 | 2016-01-20 | 浙江师范大学 | A kind of holey gold-nano-piece array and preparation method thereof |
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