CN102274977B - Method for preparing synthesized cobalt-gold double-metal alloy nano particle - Google Patents
Method for preparing synthesized cobalt-gold double-metal alloy nano particle Download PDFInfo
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Abstract
The invention provides a method for preparing a synthesized cobalt-gold double-metal alloy nano particle and belongs to the technical field of inorganic material preparation processes. The method comprises the following steps of: 1, adding polyvinylpyrrolidone and inorganic salt of cobalt into an ethylene glycol solvent to obtain mixed solution; 2, under the condition of stirring, adding hydrazine hydrate and ethylene glycol solution of chloroauric acid into the mixed solution sequentially; and 3, removing a heating source after the reaction is stopped, performing centrifugal separation, collection and deposition, washing by using ethanol and drying. The cobalt-gold double-metal alloy nano particle prepared by using the method for preparing the synthesized cobalt-gold double-metal alloy nano particle has the characteristic of a chain structure. In the method, inorganic substances are used as raw materials, so the reaction is low in toxicity and the raw materials are more economical; the cobalt and the gold of the product are distributed uniformly, and a proportion of the cobalt to the gold can be regulated within a certain range; moreover, the reaction time is short, the process is simple and the production can be enlarged easily.
Description
Technical field
The present invention relates to a kind of preparation method of synthetic cobalt gold bimetallic alloy nano particle, belong to the inorganic compound semiconductor technical field of material.
Background technology
Gold will not only may realize that light-magnetic function is compound with the compound of magnetic nano-particle, and help to overcome the shortcomings such as easy reunion that magnetic nano-particle exists and poor chemical stability in application, have huge application prospect in fields such as catalysis, biomedicines (as: biology/chemical sensitisation, imaging, medical diagnosis on disease and drug delivery).In recent years, the synthetic and property research of gold/magnetic nano particle compound become international research frontier a focus.
The used method of preparation of gold/magnetic metal compound is mainly oxidation-reduction method at present, namely take comparatively active magnetic metal particle as certainly sacrificing template, to wherein adding the gold chloride ion, by the intermetallic displacement reaction, prepare and have the nano-complex that magnetic is examined golden shell structure.Such as: the grand teach problem group of Chinese University of Science and Technology's Yu's book take the Co nanosphere for preparing in advance as from sacrificing template, by the intermetallic displacement reaction, in the presence of polyvinylpyrrolidone (PVP), prepared Co/Au yolk type nucleocapsid structure, studies show that product has application potential (Adv.Mater.22 volume aspect bio-molecular separation, 1407 pages, 2010).Tanaka group's teach problem group of Xiamen University has prepared Au/M (M=Co, Ni) nucleocapsid structure, studies show that the formation of nucleocapsid structure makes Co, and it is 10 that the weak surface-enhanced Raman signal of Ni script is increased to enhancer
3～10
4(J.Phys.Chem.C 112 volumes, 345 pages, 2008 .).Although this method is obtaining some successful examples in preparation aspect gold/magnetic metal complex nano material, yet, because the shortcoming such as the limitation of method exists the products therefrom structure single, and the component adjustability is poor has influence on performance and the application of material.
Summary of the invention
For problems of the prior art, the present invention proposes a kind of preparation method of synthetic cobalt gold bimetallic alloy nano particle, the method have equipment simple, be easy to realize the advantages such as control, good process repeatability, constant product quality.
The preparation method of a kind of synthetic cobalt gold bimetallic alloy nano particle that the present invention proposes adopts chemical solution method, specifically comprises following step:
Step 1: to the middle inorganic salts that add polyvinylpyrrolidone (PVP) and cobalt of ethylene glycol solvent (purity is greater than 98%), the mol ratio of the inorganic salts of polyvinylpyrrolidone (PVP) and cobalt is 0.5: 1～3: 1, the cobalt ions molar concentration is 0.01～0.05mol/L, obtains mixed liquor.The inorganic salts of described cobalt are selected from any one in cobalt chloride, cobalt acetate, the cobalt nitrate.
Step 2: under stirring condition, in mixed liquor, add 1.5～3.0mL hydrazine hydrate (mass fraction is more than or equal to 50%), after stirring, obtain pink turbid solution, continue under stirring condition, to wherein further the admixture mass concentration be 1 * 10
-4～1 * 10
-2Mol/L (is preferably 5 * 10
-3Mol/L) ethylene glycol solution of gold chloride, keep that the mol ratio of cobalt ions and gold ion is 1: 1～10: 1 in the solution, solution becomes bluish violet by pink, is under 160 ℃～195 ℃ the temperature in reaction temperature, reacted 1～2 hour, and occurred black precipitate in the solution.Described stirring condition can be the mode of magnetic agitation, mechanical agitation or ultrasonic concussion, and the inorganic salts of gold chloride and cobalt are dispersed in the solvent.
Step 3: remove heating source after reaction stops, after the question response liquid cooling but, the centrifugation collecting precipitation, be placed in the baking oven dry with ethanol (purity is greater than 98%) washing (preferably washing more than three times with ethanolic solution), baking temperature is 40 ℃～60 ℃, 4-8 hour drying time, namely obtain cobalt gold bimetallic alloy nano particle.
The preparation-obtained product cobalt gold of the preparation method bimetallic alloy nano particle of a kind of synthetic cobalt gold bimetallic alloy nano particle that proposes by the present invention has the chain structure feature.
The invention has the advantages that:
1, the present invention proposes a kind of preparation method of synthetic cobalt gold bimetallic alloy nano particle, and the employing inorganic matter is raw material, and the reaction toxicity of the method is little, and raw material is more economical;
2, the present invention proposes a kind of preparation method of synthetic cobalt gold bimetallic alloy nano particle, and cobalt evenly distributes with gold in the products therefrom, and within the specific limits cobalt, golden ratio is adjustable; Products obtained therefrom has larger performance regulation and control space, can be by regulating the composition of alloy, and namely the ratio of cobalt, gold makes its magnetic performance adjusted in the alloy.
3, the present invention proposes a kind of preparation method of synthetic cobalt gold bimetallic alloy nano particle, and the reaction time is short, and technique is quite simple, produces to be easy to amplify, and lays a good foundation for this preparation method is applied to industrial production.
Description of drawings
Fig. 1: the preparation method's of a kind of synthetic cobalt gold bimetallic alloy nano particle that the present invention proposes flow chart;
Fig. 2: the transmission electron microscope photo of the embodiment of the invention 1 resulting cobalt gold bimetallic alloy nano particle.
Fig. 3: the EDS constituent analysis figure of the embodiment of the invention 1 resulting cobalt gold bimetallic alloy nano particle.
Fig. 4: the transmission electron microscope photo of the embodiment of the invention 2 resulting cobalt gold bimetallic alloy nano particles.
Fig. 5: the EDS constituent analysis figure of the embodiment of the invention 2 resulting cobalt gold bimetallic alloy nano particles.
Fig. 6: the X-ray powder diffraction pattern (XRD) of the cobalt gold bimetallic alloy nano particle of two kinds of heterogeneity ratios that the embodiment of the invention 1 and 2 obtains.
The specific embodiment
The present invention is described in detail below in conjunction with drawings and Examples.
The preparation method of a kind of synthetic cobalt gold bimetallic alloy nano particle that the present invention proposes adopts chemical solution method, as shown in Figure 1, specifically comprises following step:
Step 1: to the middle inorganic salts that add polyvinylpyrrolidone (PVP) and cobalt of ethylene glycol solvent (purity is greater than 98%), the mol ratio of the inorganic salts of polyvinylpyrrolidone (PVP) and cobalt is 0.5: 1～3: 1, the cobalt ions molar concentration is 0.01～0.05mol/L, obtains mixed liquor.The inorganic salts of described cobalt are selected from any one in cobalt chloride, cobalt acetate, the cobalt nitrate.
Step 2: under stirring condition, in mixed liquor, add 1.5～3.0mL hydrazine hydrate (mass fraction is more than or equal to 50%), after stirring, obtain pink turbid solution, continue under stirring condition, to wherein further the admixture mass concentration be 1 * 10
-4～1 * 10
-2Mol/L (is preferably 5 * 10
-3Mol/L) ethylene glycol solution of gold chloride, keep that the mol ratio of cobalt ions and gold ion is 1: 1～10: 1 in the solution, solution becomes bluish violet by pink, is under 160 ℃～195 ℃ the temperature in reaction temperature, reacted 1～2 hour, and occurred black precipitate in the solution.Described stirring condition can be the mode of magnetic agitation, mechanical agitation or ultrasonic concussion, and the inorganic salts of gold chloride and cobalt are dispersed in the solvent.
Step 3: remove heating source after reaction stops, after the question response liquid cooling but, the centrifugation collecting precipitation, be placed in the baking oven dry with ethanol (purity is greater than 98%) washing (preferably washing more than three times with ethanolic solution), baking temperature is 40 ℃～60 ℃, 4-8 hour drying time, namely obtain cobalt gold bimetallic alloy nano particle.
The preparation-obtained product cobalt gold of the preparation method bimetallic alloy nano particle of a kind of synthetic cobalt gold bimetallic alloy nano particle that proposes by the present invention has the chain structure feature.
Embodiment 1:
The preparation method of a kind of synthetic cobalt gold bimetallic alloy nano particle that the present embodiment proposes specifically comprises following step:
Step 1: in 10mL ethylene glycol solvent (purity is greater than 98%), add 0.011g polyvinylpyrrolidone (PVP) and 0.018g cobalt acetate, the mol ratio of polyvinylpyrrolidone (PVP) and cobalt acetate is 1: 1, the cobalt ions molar concentration is 0.01mol/L, obtains mixed liquor.
Step 2: under stirring condition, in mixed liquor, add 1.5mL hydrazine hydrate (mass fraction equals 50%), after stirring, obtain pink turbid solution, under stirring condition, continue to the ethylene glycol solution (5 * 10 that wherein further adds the 20mL gold chloride
-3Mol/L), keep that the mol ratio of cobalt ions and gold ion is 1: 1 in the solution, solution becomes bluish violet by pink, with the electric jacket heating, is under 195 ℃ the temperature, to react 2 hours in reaction temperature, occurs black precipitate in the solution.Described stirring condition is mechanical agitation, and the inorganic salts of gold chloride and cobalt are dispersed in the solvent.
Step 3: remove heating source after reaction stops, after the question response liquid cooling but, the centrifugation collecting precipitation, be placed in the baking oven dry with ethanol (purity is greater than 98%) washing three, baking temperature is 60 ℃, obtain dry and comfortable black powder 4 hours drying times, i.e. cobalt gold bimetallic alloy nano particle.
The cobalt for preparing gold bimetallic alloy nano particle is carried out transmission electron microscope observing, and as shown in Figure 2, it is chain structure about 20nm that the cobalt gold bimetallic alloy nano particle for preparing is particle diameter.The cobalt gold bimetallic alloy nano particle for preparing is carried out the EDS atlas analysis, and as shown in Figure 3, the atom number ratio of Co and Au is Co/Au=3 in the cobalt gold bimetallic alloy nano particle for preparing: 2.
Embodiment 2:
The preparation method of a kind of synthetic cobalt gold bimetallic alloy nano particle that the embodiment of the invention proposes specifically comprises following step:
Step 1: to 20mL ethylene glycol solution (purity is greater than 98%), then to wherein adding 0.33g polyvinylpyrrolidone (PVP) 0.239g cobalt chloride hexahydrate, the mol ratio of the inorganic salts of polyvinylpyrrolidone (PVP) and cobalt is 3: 1, the cobalt ions molar concentration is 0.05mol/L, obtains mixed liquor.
Step 2: under stirring condition, in mixed liquor, add 1.5～3.0mL hydrazine hydrate (mass fraction is more than or equal to 50%), after stirring, obtain pink turbid solution, continuation is under stirring condition, to the ethylene glycol solution (5 * 10 that wherein further adds the 20mL gold chloride
-3Mol/L), keeping that the mol ratio of cobalt ions and gold ion is 10: 1 in the solution, is under 160 ℃ the temperature, to react 2 hours in reaction temperature.Described stirring condition is magnetic agitation.
Step 3: remove heating source after reaction stops, after the question response liquid cooling but, the centrifugation collecting precipitation, be placed on for three times in the baking oven dry with ethanol (purity is greater than 98%) washing, baking temperature is 40 ℃, obtain dry and comfortable black powder 8 hours drying times, namely obtains cobalt gold bimetallic alloy nano particle.
The transmission electron microscope photo of cobalt gold bimetallic alloy nano particle as shown in Figure 4 can be found out, prepared gadolinium obtains cobalt gold bimetallic alloy nano particle and is the chain structure of particle diameter about 20nm.The EDS collection of illustrative plates of cobalt gold bimetallic alloy nano particle alloy nano particle as shown in Figure 5 can find out the product that from analysis result the atom number of Co and Au is than being Co/Au=4: 1.The X-ray powder diffraction pattern of the cobalt of two kinds of heterogeneity ratios that embodiment 1 and 2 obtains gold bimetallic alloy nano particle as shown in Figure 6, as can be seen from the figure the X-ray powder diffraction pattern of product with the two-phase of the X-ray powder diffraction pattern of Co (JCPDS No.01-1259) and Au (JCPDS No.04-0784) is compound can well be corresponding.Compare with single-phase Co, Au, the X-ray powder diffraction peak-to-peak position of product is not offset, and this shows and does not form the AuCo intermetallic compound in the product, Au and Co disorder distribution in product.
Embodiment 3:
The preparation method of a kind of synthetic cobalt gold bimetallic alloy nano particle that the embodiment of the invention proposes specifically comprises following step:
Step 1: in ethylene glycol solvent (purity is greater than 98%), add polyvinylpyrrolidone (PVP) and cobalt acetate, the mol ratio of polyvinylpyrrolidone (PVP) and cobalt acetate is 0.5: 1, the cobalt ions molar concentration is 0.01mol/L, obtains mixed liquor.
Step 2: under stirring condition, add 1.5mL hydrazine hydrate (mass fraction equals 50%) in the mixed liquor, after stirring, obtain pink turbid solution, continue under stirring condition, to wherein further the admixture mass concentration be 1 * 10
-4The ethylene glycol solution of the gold chloride of mol/L keeps that the mol ratio of cobalt ions and gold ion is 1: 1 in the solution, and solution becomes bluish violet by pink, in reaction temperature is under 160 ℃ the temperature, to react 1 hour, occurs black precipitate in the solution.
Step 3: after stopping, reaction removes heating source, after the question response liquid cooling but, the centrifugation collecting precipitation, be placed on for three times in the baking oven dry with ethanol (purity is greater than 98%) washing, baking temperature is 40 ℃, 4 hours drying times, namely obtains cobalt gold bimetallic alloy nano particle.
Embodiment 4:
The preparation method of a kind of synthetic cobalt gold bimetallic alloy nano particle that the embodiment of the invention proposes specifically comprises following step:
Step 1: in ethylene glycol solvent (purity is greater than 98%), add polyvinylpyrrolidone (PVP) and cobalt nitrate, the mol ratio of polyvinylpyrrolidone (PVP) and cobalt nitrate is 3: 1, the cobalt ions molar concentration is 0.05mol/L, obtains mixed liquor.The inorganic salts of described cobalt are selected from any one in cobalt chloride, cobalt acetate, the cobalt nitrate.
Step 2: under stirring condition, in mixed liquor, add 3.0mL hydrazine hydrate (mass fraction equals 60%), after stirring, obtain pink turbid solution, continue under stirring condition, to wherein further adding 1 * 10
-2The ethylene glycol solution of the gold chloride of mol/L keeps that the mol ratio of cobalt ions and gold ion is 5: 1 in the solution, and solution becomes bluish violet by pink, in reaction temperature is under 180 ℃ the temperature, to react 1.5h hour, occurs black precipitate in the solution.
Step 3: after stopping, reaction removes heating source, after the question response liquid cooling but, the centrifugation collecting precipitation, be placed on for four times in the baking oven dry with ethanol (purity is greater than 98%) washing, baking temperature is 50 ℃, 6 hours drying times, namely obtains cobalt gold bimetallic alloy nano particle.
Embodiment 5:
The preparation method of a kind of synthetic cobalt gold bimetallic alloy nano particle that the embodiment of the invention proposes specifically comprises following step:
Step 1: in ethylene glycol solvent (purity is greater than 98%), add polyvinylpyrrolidone (PVP) and cobalt chloride, the mol ratio of polyvinylpyrrolidone (PVP) and cobalt chloride is 2: 1, the cobalt ions molar concentration is 0.03mol/L, obtains mixed liquor.
Step 2: under stirring condition, in mixed liquor, add 2.0mL hydrazine hydrate (mass fraction equals 50%), after stirring, obtain pink turbid solution, continue under stirring condition, to wherein further adding 1 * 10
-3The ethylene glycol solution of mol/L gold chloride keeps that the mol ratio of cobalt ions and gold ion is 10: 1 in the solution, and solution becomes bluish violet by pink, in reaction temperature is under 195 ℃ the temperature, to react 2 hours, occurs black precipitate in the solution.
Step 3: after stopping, reaction removes heating source, after the question response liquid cooling but, the centrifugation collecting precipitation, be placed in the baking oven dry with ethanol (purity is greater than 98%) washed twice, baking temperature is 60 ℃, 8 hours drying times, namely obtains cobalt gold bimetallic alloy nano particle.
Claims (5)
1. the preparation method of a synthetic cobalt gold bimetallic alloy nano particle is characterized in that: specifically comprise following step:
Step 1: add the inorganic salts of polyvinylpyrrolidone and cobalt in the ethylene glycol solvent, the mol ratio of the inorganic salts of polyvinylpyrrolidone and cobalt is 0.5:1～3:1, and the cobalt ions molar concentration is 0.01 ~ 0.05mol/L, obtains mixed liquor;
Step 2: under stirring condition, in mixed liquor, add 1.5 ~ 3.0mL hydrazine hydrate, after stirring, obtain pink turbid solution, continue under stirring condition, to the ethylene glycol solution that wherein further adds gold chloride, keep that the mol ratio of cobalt ions and gold ion is 1:1 ~ 10:1 in the solution, solution becomes bluish violet by pink, is under 160 ℃～195 ℃ the temperature in reaction temperature, reacted 1 ~ 2 hour, and occurred black precipitate in the solution;
Step 3: remove heating source, after the question response liquid cooling but, the centrifugation collecting precipitation is placed on drying in the baking oven with the ethanolic solution washing, obtains cobalt gold bimetallic alloy nano particle, and cobalt gold bimetallic alloy nano particle has the chain structure feature.
2. the preparation method of a kind of synthetic cobalt gold bimetallic alloy nano particle according to claim 1, it is characterized in that: the inorganic salts of cobalt are selected from any one in cobalt chloride, cobalt acetate, the cobalt nitrate in the described step 1.
3. the preparation method of a kind of synthetic cobalt gold bimetallic alloy nano particle according to claim 1 is characterized in that: to be specially amount concentration be 1 * 10 to the ethylene glycol solution of gold chloride in the described step 2
-4~ 1 * 10
-2The ethylene glycol solution of the gold chloride of mol/L.
4. the preparation method of a kind of synthetic cobalt gold bimetallic alloy nano particle according to claim 1, it is characterized in that: agitating mode is magnetic agitation, mechanical agitation or ultrasonic concussion in the described step 2.
5. the preparation method of a kind of synthetic cobalt gold bimetallic alloy nano particle according to claim 1, it is characterized in that: baking temperature is 40 ℃～60 ℃ in the described step 3,4-8 hour drying time.
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| CN102962474B (en) * | 2012-12-13 | 2014-10-22 | 北京航空航天大学 | Controllable synthetic method for preparing gold-nickel core-shell nanostructure with ethylene glycol system |
| CN105845154B (en) * | 2016-03-22 | 2018-08-07 | 武汉理工大学 | A kind of disks and preparation method thereof of large capacity long-life |
| CN106984829B (en) * | 2017-05-03 | 2019-03-22 | 厦门大学 | A kind of synthetic method of the FeCoNi ternary asymmetric particle of core-shell structure |
| CN108788126B (en) * | 2018-06-20 | 2020-02-07 | 陕西理工大学 | Preparation method of cobalt nano magnetic material |
| CN113789172B (en) * | 2021-09-10 | 2022-06-17 | 江南大学 | Composite chiral nano assembly and preparation method and application thereof |
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