CN103418800B - A kind of preparation method of nanometer gold - Google Patents
A kind of preparation method of nanometer gold Download PDFInfo
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- CN103418800B CN103418800B CN201310304293.8A CN201310304293A CN103418800B CN 103418800 B CN103418800 B CN 103418800B CN 201310304293 A CN201310304293 A CN 201310304293A CN 103418800 B CN103418800 B CN 103418800B
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Abstract
The preparation method that the invention discloses a kind of nanometer gold, the method is with monovalence gold complex for raw material, using water and molecular weight less than one or both in the hydrophilic organic solvent of 100 as solvent, add raw materials into and solvent obtains reactant liquor, the monovalence gold concentration controlled in reactant liquor is 0.1 gram liter～2 gram liter, and temperature is 80 DEG C～95 DEG C, and pH value is 0.3～1.5, reaction 3min～20min obtains nanometer gold product, and the particle size distribution range of product is 5nm～15 nm.The feature of the method is: 1) preparation process is without additionally adding reducing agent, saving energy and reduce the cost, 2) not chloride ion-containing or other halogen species in raw materials used, decrease the waste discharge of nanometer gold preparation process, simplify the purge process of nanometer gold product, 3) moderate in grain size of gained nanogold particle, narrow distribution.
Description
Technical field
The present invention relates to the preparation field of a kind of nanometer gold, the preparation method being specifically related to a kind of nanometer gold.
Background technology
Nanometer gold is widely used in the fields such as optical probe, electrochemical probe, DNA detection and other biochemical analysis, colloidal sol, commodity inspection, medicine, catalyst, plant protection due to the electrical property of its excellence, optical property and surface property, all needs to use nanometer gold.But, if from the preparation method of nanometer gold, almost all adopt gold using the Auric chloride. of positive trivalent existence, gold chloride and its esters (such as sodium chloraurate or ammonium chloraurate or potassium chloroaurate etc.) as its raw material (or claim parent compound, Jin Yuan), its limitation is fairly obvious, because trivalent gold has uncertain namely it is also possible to generate sub-gold product in being reduced process, the not all subsequent handling of chloride ion of Jin Yuanzhong is all welcome, and will remove and totally be not easy very much；Adopting gold chloride and its esters is that often the outer adding citric acid of palpus and salt or other reducing agent thereof could obtain the nanometer gold of zeroth order as another restriction of Jin Yuan, these additional reducing agents (and the variant being aoxidized by trivalent gold and producing) make the composition of preparation system tend to complicating, and subsequent concentration, purification and application all only have negative impact undoubtedly.
Application number is the patent (Yang Hui of 201110122832.7, poplar changes, a kind of preparation method of nanometer gold, application number 201110122832.7, Authorization Notice No. CN102218542B, authorized announcement date 20130410) describe with chloride trivalent gold compound for Jin Yuan, using water be solvent, by reducing agents such as carbamide, chloride trivalent gold compound is reduced, Polyethylene Glycol as dispersant preparing nano gold method, gained nanometer gold uniform particle sizes disclosed in literary composition, but particle diameter is relatively big, is 20～30nm.Application number a kind of method adopting ultrasonic-electrochemistry coupling technique to prepare nanometer gold that has been the patent Introduction of CN201210274553.7, this method is with gold chloride for raw material, add a certain amount of surfactant, aqueous phase carries out, based on electrodeposition technology, ultrasonic technology is applied in the preparation of nanometer gold；By having regulated and controled ultrasonic frequency, groove pressure, die opening and electrodeposition time disclosed in literary composition, it may be achieved the control of nanometer film pattern；There is technique simple, it is not necessary to the features such as additional reducing agent, but do not report the productivity of nanometer gold product, nanometer gold can be carried out as the technology of a kind of practicality and produce the inspection needing to accept the time.Application number a kind of nanometer gold preparation method that has been the patent Introduction of CN201110089033.4, it adopts peroxycarbonate to be reducing agent, and fluorine-containing surfactant (Zonly-FSN) is stabilizer, prepares ball-type nano gold sol；Wherein peroxycarbonate is to be simultaneously introduced hydrogen peroxide and bicarbonate in reactant liquor in preparation process and produce, disclosed in literary composition, this method can control the amount of the peroxycarbonate in course of reaction by controlling the addition of bicarbonate, it is finally reached the purpose controlling nanometer gold size, but, if chloride ion is still mixed is it will be evident that remove it clean quite difficulty in the product.Application number is the patent of 201310064454.0, describes a kind of method utilizing gas-phase deposition to prepare nanometer gold；It is characterized in that: using the gold of purity 99.99% as raw material, d.c. sputtering different time obtains different-thickness nano-Au films, is then annealed in uniform temperature and time range, can obtain various sizes of nanogold particle disclosed in literary composition, but, the quality of nanometer gold and productivity are also unintelligible.Application number is the patent of 20111016420.2, describes with gold chloride for raw material, adopts organic amine and aldehyde compound as the reducing agent method to prepare nanometer gold；Obviously, the toxicity of organic amine and aldehyde compound and they be fairly obvious to the difficulty that nanometer gold purifying products brings.
Therefore, develop new nanometer gold preparation method, raw material is the solubility auro compound of not chloride ion-containing, it is not necessary to additionally adds reducing agent, reduces nanometer gold preparation process waste discharge, significant.
Summary of the invention
For the deficiencies in the prior art, the preparation method that it is an object of the invention to provide a kind of nanometer gold, the method raw material is the solubility auro compound of not chloride ion-containing, without additionally adding reducing agent, reducing nanometer gold preparation process waste discharge, and product cut size is little, the response time is short.
For reaching above-mentioned purpose, the technical solution adopted in the present invention is:
A kind of preparation method of nanometer gold, with monovalence gold complex for raw material, using water and molecular weight less than one or both in the hydrophilic organic solvent of 100 as solvent, add raw materials in solvent, obtaining reactant liquor, controlling monovalence gold concentration in reactant liquor is 0.1 gram liter～2 gram liter, and temperature is 80 DEG C～95 DEG C, pH value is 0.3～1.5, and reaction 3min～20min obtains nanometer gold product；The formula of described monovalence gold complex is Mr[AuL2]q . xH2O, wherein: L represents inferior sulfate radical, it is the anion with two negative charges, and 2 is the ligancy of L, the golden complex anion [AuL of negative trivalent2]-3Being its core ingredient, q represents [AuL in such gold complex2]-3Quantity, q be not equal to zero positive integer；M represents and [AuL2]-3Balance cation, r represents this cationic number, r be not equal to zero positive integer；X represents the quantity of water of crystallization, and x is 0 or positive integer.
Described M is preferably potassium, sodium or ammonium.
Described monovalence gold complex is preferably inferior sulfate radical Asia gold potassium (K3Au(SO3)2 . xH2O, x represent the quantity of water of crystallization, x be 0 or positive integer), inferior sulfate radical Asia gold sodium (Na3Au(SO3)2 . xH2O, x represent the quantity of water of crystallization, x be 0 or positive integer) or inferior sulfate radical Asia gold ammonium ((NH4)3Au(SO3)2, . xH2O, x represent the quantity of water of crystallization, x be 0 or positive integer), and aqueous containing above-mentioned sub-gold complex or its solution.
Described hydrophilic organic solvent is preferably alcohol or ketone, more preferably ethanol.
In described reactant liquor, monovalence gold concentration is preferably 0.5 gram liter～1.5 gram liter.
Preferably add the dispersant of 0.1 times relative to the golden amount of monovalence in raw material～2 times in a solvent.Described dispersant is preferably one or more in Polyethylene Glycol, carbamide and polyvinylpyrrolidone (being commonly called as PVP).
The particle size distribution range of described nanometer gold product is preferably 5nm～15nm.
The present invention will be further explained below:
The present invention is new method prepared by a kind of nanometer gold, one of feature: adopt not halogen-containing solubility monovalence gold (i.e. sub-gold) complex as raw material.It is the process of reduction in a molecule that this patent generates the process of nanometer gold, in the process of such a generation nanometer gold (namely monovalence gold is reduced to zeroth order gold), inferior sulfate radical in complex is correspondingly changed into sulfate radical, they are all the anion of gentleness, to subsequent applications (such as gilding etc.) without negative effect (plating of industrial employing sulfuric acid system and few be best evidence with hydrochloric acid system plating), even if it is also simple than chloride ion to separate them, because their anion weight is also twice than chloride ion more than chloride ion and charge number.Therefore this preparation method that the present invention introduces can not additional reducing agent, reduce production cost, simplify the composition of the preparation system i.e. not halogen species such as chloride ion-containing, also mitigate the pressure separating purge process simultaneously, because a lot of application industries (such as gilding etc.) are that the halide ions such as chloride ion are abstained from very much, therefore it is the incomparable as waste nanometer gold method using gold chloride or its associated salts of routine.By the nanometer gold of this law gained all not chloride ion-containing and other halide ion in the whole course of processing, solve chloride ion in conventional preparation process to be very difficult to remove clean deficiency, decrease nanometer gold preparation process waste discharge, preparation-obtained use is by more, and the environment protection treating of the waste water after nanometer gold processed is also relatively easy.
The two of feature: the present invention controls to generate the shape of nanogold particle, formation speed and particle diameter by controlling the adjustment of technological parameter (such as temperature, time, pH etc.), thus is conducive to variation and the steady quality of nanometer gold product.Additionally, the present invention also has the hydrophilic organic solvent that can adopt non-water as the convenience of solvent, they are to the concentration of nanometer gold product, dry also useful.
The three of feature: this nanometer gold particle diameter done by the present invention is little; narrowly distributing; within the scope of 5nm～15nm; can be applicable to: the fields such as medicine, catalyst, optical probe, DNA detection and other biochemical analysis, sensor, electrochemical probe, plant protection, it is possible to be used for the synthesis of other gold complex as Jin Yuan.
Compared with prior art, the advantage of the present invention is:
1, the preparation method of the nanometer gold of the present invention, raw material is the solubility auro compound of not chloride ion-containing, it is not necessary to additionally add reducing agent, reduces purifying products and the waste discharge of nanometer gold preparation process.
2, the preparation-obtained product cut size narrowly distributing (5～15nm) of the preparation method of the nanometer gold of the present invention, it is simple to application.
3, in the preparation process of the nanometer gold of the present invention, the response time is short, stable reaction conditions, easily-controllable.
Accompanying drawing explanation
Fig. 1 is the TEM(transmission electron microscope of nanometer gold product in embodiment) figure；
Fig. 2 is the UV(uv-vis spectra of nanometer gold product in embodiment) figure；
Fig. 3 is the grain size distribution of nanometer gold product in embodiment.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further.Described in embodiment, percentage composition is weight/mass percentage composition.
Embodiment 1:
Institute's Sheng container is the container after having carried out silicidation, by inferior sulfate radical Asia gold potassium [chemical formula: K3Au(SO3)2], weigh 0.5 gram and be dissolved in containing 0.1 gram of PEG(Polyethylene Glycol, MW400), 75 milligrams of PVP(polyvinylpyrrolidone-K30), in 500 grams of DI water, mixing speed is maintained in the scope of 250～400rpm, the pH value of said mixture is regulated to 1～1.5 by the dilute sulfuric acid with 5%, by the mode indirectly heated, the temperature of said mixture is regulated within the scope of 85～95 DEG C, find after 1 minute that the color of above-mentioned reaction solution constantly changes as generated aubergine etc., the transparency of reactant liquor also constantly declines, find above-mentioned reaction vessel generates nanometer gold product after 5 minutes.Adopt TEM (transmission electron microscope) that the nanometer gold product in above-mentioned reactor has been detected, as shown in Figure 1, it has been found that their particle diameter is mainly distributed within the scope of 5～15nm, granule shape spherical in shape；Adopt UV (uv-vis spectra) that the nanometer gold product in above-mentioned reactor has been detected, as shown in Figure 2, it has been found that they characteristic absorption occur near 520nm, meet the characteristic of nanometer gold；Adopt Mastersizer2000 laser diffraction granularity analyser that the particle size distribution of above-mentioned nanometer gold product has been detected, find that their particle diameter is mainly distributed on 5～15nm scope and in normal distribution, as it is shown on figure 3, illustrate can prepare without halide ion, particle size distribution range is narrow, particle uniformity is good ball shaped nano gold product by this law.
Embodiment 2:
Institute's Sheng container is the container after having carried out silicidation, takes inferior sulfate radical Asia gold sodium [chemical formula: Na3Au(SO3)2] weigh 0.45 gram and be dissolved in 300 grams of DI water, it is added thereto to 0.05 gram of PEG(Polyethylene Glycol, MW600), 60 milligrams of PVP(polyvinylpyrrolidone-K30), it is settled to 500 milliliters with DI water, mix within the scope of the mixing speed of 250～400rpm, and with the dilute sulfuric acid of 5%, the pH value of said mixture is regulated and controled 0.5～1.2, by in the way of indirectly heating by the temperature adjusting of said mixture within the scope of 80～90 DEG C, find after 4 minutes that change occurs in the color of above-mentioned reaction solution, the transparency of reaction system constantly declines, find after 7 minutes above-mentioned reaction vessel generates nanogold particle.Adopt UV (uv-vis spectra) that the nanometer gold product in above-mentioned reactor has been detected, it has been found that they characteristic absorption occur near 520nm, meet the characteristic of nanometer gold；Adopt TEM (transmission electron microscope) that the nanometer gold product in above-mentioned reactor has been detected, it has been found that the granule shape spherical in shape of nanometer gold product；Centralized particle diameter, in the scope of 5～15nm.Illustrate to prepare the ball shape nanometer gold product without halide ion, narrow diameter distribution by this law.
Embodiment 3:
Institute's Sheng container is the container after having carried out silicidation, takes inferior sulfate radical Asia gold ammonium [chemical formula: (NH4)3Au(SO3)2,] weigh 0.48 gram and be dissolved in the mixed solvent being made up of 150 milliliters of DI water and 75 milliliters of ethanol, it is added thereto to 0.05 gram of PEG(Polyethylene Glycol, MW600), 0.2 gram of carbamide and 52 milligrams of PVP(polyvinylpyrrolidone-K30), it is settled to 500 milliliters with " water-ethanol " mixed solvent of above-mentioned identical proportioning, mix within the scope of the mixing speed of 220～330rpm, and with the dilute sulfuric acid of 5%, the pH value of said mixture is regulated and controled 0.8～1.3, by in the way of indirectly heating by the temperature adjusting of said mixture within the scope of 85～95 DEG C, find after 3 minutes that change occurs in the color of above-mentioned reaction solution, the transparency of reaction system constantly declines, find after 6 minutes above-mentioned reaction vessel generates nanogold particle.Adopt UV (uv-vis spectra) that the nanometer gold product in above-mentioned reactor has been detected, it has been found that they characteristic absorption occur near 520nm, meet the characteristic of nanometer gold；Adopt TEM (transmission electron microscope) that the nanometer gold product in above-mentioned reactor has been detected, it has been found that in their particle diameter is main peak with 10nm, is mainly distributed on the scope of 5～15nm.Illustrating can prepare without halide ion, particle size distribution by this law is the ball shaped nano gold product of normal distribution.
Claims (7)
1. the preparation method of a nanometer gold, it is characterized in that, with monovalence gold complex for raw material, using water and molecular weight less than one or both in the hydrophilic organic solvent of 100 as solvent, adding raw materials into and obtain reactant liquor in solvent, controlling monovalence gold concentration in reactant liquor is 0.1 gram liter～2 gram liter, and temperature is 80 DEG C～95 DEG C, pH value is 0.3～1.5, and reaction 3min～20min obtains nanometer gold product；The formula of described monovalence gold complex is Mr[AuL2]q . xH2O, wherein: L represents inferior sulfate radical, it is the anion with two negative charges, and 2 is the ligancy of L, the golden complex anion [AuL of negative trivalent2]-3Being its core ingredient, q represents [AuL in such gold complex2]-3Quantity, q be not equal to zero positive integer；M represents and [AuL2]-3Balance cation, r represents this cationic number, r be not equal to zero positive integer；X represents the quantity of water of crystallization, and x is 0 or positive integer；Described hydrophilic organic solvent is alcohol or ketone.
2. the preparation method of a kind of nanometer gold according to claim 1, is characterized in that, described M is potassium, sodium or ammonium.
3. the preparation method of a kind of nanometer gold according to claim 1, is characterized in that, monovalence gold complex is inferior sulfate radical Asia gold potassium, inferior sulfate radical Asia gold sodium or inferior sulfate radical Asia gold ammonium.
4. the preparation method of a kind of nanometer gold according to claim 1 or claim 2, is characterized in that, in described reactant liquor, monovalence gold concentration is 0.5 gram liter～1.5 gram liter.
5. the preparation method of a kind of nanometer gold according to claim 1 or claim 2, is characterized in that, adds the dispersant relative to the golden amount of monovalence in raw material 0.1 times～2 times in a solvent.
6. the preparation method of a kind of nanometer gold according to claim 5, is characterized in that, described dispersant is one or more in Polyethylene Glycol, carbamide and polyvinylpyrrolidone.
7. the preparation method of a kind of nanometer gold according to claim 1 or claim 2, is characterized in that, the particle size distribution range of described nanometer gold product is 5nm～15nm.
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| CN108420748B (en) * | 2018-04-25 | 2021-11-30 | 上海谦懋纺织科技有限公司 | Processing technology of blue copper peptide combined with nano gold and nano diamond structure |
| CN109175395B (en) * | 2018-09-29 | 2022-02-08 | 岭南师范学院 | Green controllable synthesis method of nanogold and one-step peptide functionalization method thereof |
| CN113996802A (en) * | 2021-11-02 | 2022-02-01 | 太原工业学院 | Preparation method of cubic copper nanoparticles |
| CN114682791A (en) * | 2022-03-31 | 2022-07-01 | 长沙新材料产业研究院有限公司 | Gold nanoparticle dispersion, gold nanoparticles and preparation method thereof |
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| ES2335467B1 (en) * | 2008-09-22 | 2010-12-30 | Consejo Superior De Investigaciones Cientificas (Csic) (10%) | SYNTHESIS OF SUBNANOMETRIC PARTICLES OF AU CATALITICS SUPPORTED IN SURFACES WITH AMINO GROUPS. |
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| CN102218542A (en) * | 2011-05-12 | 2011-10-19 | 陕西科技大学 | Nanogold preparation method |
| CN102976360A (en) * | 2012-11-22 | 2013-03-20 | 长沙铂鲨环保设备有限公司 | Thiocyanate-containing gold complex as well as preparation method and application thereof |
| CN102990082A (en) * | 2012-12-17 | 2013-03-27 | 桂林理工大学 | Method for preparing fluorescence nano gold sol by using PVP (Poly Vinyl Pyrrolidone) through reduction modification under hydrothermal condition |
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