CN102380620A - Method for preparing magnetic metal-metal core-shell nano particles - Google Patents
Method for preparing magnetic metal-metal core-shell nano particles Download PDFInfo
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Abstract
The invention discloses a method for preparing magnetic metal-metal core-shell nano particles, which relates to metal nano particles. The method comprises: dissolving chloroauric acid and triphenylphosphine in ethanol respectively, filtering, cleaning, drying, obtaining an organic compound formed by gold and triphenylphosphine, mixing the organic compound with alkylamine, obtaining solution A, mixing an organic solvent A with a noble metal salt, adding mixed solution A, rising the temperature to perform a reaction, cooling and obtaining magnetic metal nano particles; dissolving the obtained organic compound formed by gold and triphenylphosphine in an organic solvent B, injecting obtained magnetic metal nano particles, keeping the temperature between 120 and 160 DEG C for 20 minutes to 1 hour, reducing to obtain gold and wrapping gold on the formed magnetic metal nano particles and obtaining nano particles in which gold and magnetic metal are in a core-shell structure; and washing the nano particles in which gold and magnetic metal are in a core-shell structure, performing centrifugal separation, drying and obtaining powder product, namely magnetic metal-gold core-shell nano particles.
Description
Technical field
The present invention relates to a kind of metal nanoparticle, especially relate to a kind of magnetic metal-gold core-shell type nanometer particle process method.
Background technology
Metal nanoparticle is because its size is little, and specific area is big, has the incomparable premium properties of conventional block materials; And paid attention to gradually; But its surface-active is high, is prone to reunite, and in air, is prone to oxidized; Particularly magnetic metal (Fe, Co, Ni) nano particle in air, more be prone to oxidized, big limitations its serviceability and range of application.If with the inert layer nano metallic nickel granular material coating, form nucleocapsid structure, then can solve the problem of oxidation of nano particle, and can not produce significantly influence the magnetism characteristic of particle.Therefore prepare nano metallic nickel granular material and just seem particularly important with nucleocapsid structure.
Gold not only has special optics and electrical properties, and has good catalytic activity and biomolecule affinity as a kind of noble metal, is widely used at development, catalysis and the chemical analysis of photoelectric component.Utilize golden nanometer particle can significantly increase the characteristic that spectral signal intensity perhaps changes spectrum, it is applied in the sensor that changes based on spectral characteristic; The surface plasma resonance spectrum of golden nanometer particle can be used for the analyzing and testing of DNA, can the bio-identification reaction conversions be become the optics or the electrical signal of an amplification; The characteristic of the big absorption cross-section of gold makes golden nanometer particle very low to reflection of light, and thermal transition efficient is very high, thereby can be used as photo-thermal therapy reagent.In addition, golden nanometer particle also has high chemism and catalysis characteristics.
If gold and nano metallic nickel granular material are combined, form nucleocapsid structure, just can make full use of both sides' excellent specific property.For example, the nuclear shell type nano meter particle of gold-coating magnetic property metal because particle core is a magnetic metal, thereby has the magnetic control characteristic, is convenient to handle with reclaiming and separates, and golden shell has well been protected magnetic metal nuclear not oxidized.Simultaneously, specific organic molecule and biomolecule also can be modified in the surface of gold, are convenient to realize its application biological and the medical science aspect.
Preparation report about magnetic metal-gold core-shell type nano particle is uncommon.Xu etc. (Adv.Mater.2008,20,994-999) adopt physical method (magnetron sputtering method) to prepare the nano particle of golden coating cobalt, particle diameter is totally comparatively even, but output is few, cost is high, shell is not obvious.Compare with respect to the general physical preparation method, liquid phase method has advantages such as cost is cheap relatively, the simple relatively and easy realization amplification of technology path production.Lu etc. (Adv.Mater.2010,22,1407-1411) reported the liquid phase method preparation of the core-shell nano of golden coating cobalt, the nanoparticulate dispersed property of preparing is better, but its particle diameter is bigger, surpasses 100 nanometers.Chen etc. (Chem.Mater.2007,19,3399-3405) under the water condition, prepared the nucleocapsid structure of golden coating nickel.The benefit that is equipped with the core-shell type magnetic metal nanoparticle by the water legal system is that magnetic metal salt is prone to be reduced, and reaction temperature is low, but because reduction rate is very fast, the size of nano particle and pattern are difficult to control, and shell metallic is prone to independent nucleation, and clad ratio is not high.If adopt the organic liquid phase rule to prepare the comparatively nano particle of homogeneous, advantages of good crystallization of size easily, but the generation of shell metallic control is a difficult point.The report that the nano particle of the gold-coating magnetic property metal that adopts the preparation of organic liquid phase method to provide obvious nucleocapsid structure is also still arranged at present.
Summary of the invention
The objective of the invention is to the nuclear shell type nano meter particle preparation method clad ratio of existing gold-coating magnetic property metal not high; Be difficult to obtain the deficiency of obvious nucleocapsid structure, the magnetic metal-gold core-shell type nanometer particle process method of provide a kind of and obtain to have obvious nucleocapsid structure, shell thickness is adjustable.
The present invention includes following steps:
1) 1g gold chloride and 1.36g triphenylphosphine are dissolved in respectively in 50mL and the 35mL ethanol, again product are filtered, cleans, dries, the organic compound that De Jin and triphenylphosphine form;
2) the magnetic metal precursor compound is mixed with alkylamine, get mixed liquor A, precious metal salt is mixed with organic solvent A again, after the temperature reaction of adding mixed liquor A, cooling gets nano metallic nickel granular material;
3) organic compound with resulting gold of step 1) and triphenylphosphine formation is dissolved in the organic solvent B; Implantation step 2) resulting nano metallic nickel granular material; Be incubated 20min～1h down at 120～160 ℃; Gold will be reduced out and be coated on the established nano metallic nickel granular material, obtain being the nano particle of gold and magnetic metal nucleocapsid structure;
4) nano particle that is gold and magnetic metal nucleocapsid structure with the step 3) gained cleans, centrifugation, and drying gets the powder product, magnetic metal-gold core-shell type nano particle.
In step 2) in, said the magnetic metal precursor compound is mixed with alkylamine and can under the protection of inert gas, the magnetic metal precursor compound be mixed with alkylamine; But at least a in the acetylacetonate compound of said magnetic metal precursor compound chosen from Fe, cobalt, nickel or the acetate; Said alkylamine can be selected from a kind of in oleyl amine, lauryl amine, the cetylamine etc.; Said precious metal salt can be selected from gold chloride or silver nitrate etc.; Said organic solvent A can be selected from a kind of in methyl phenyl ethers anisole, ethanol, the toluene etc.; The condition of said adding mixed liquor A temperature reaction can stir 5～30min at 50～90 ℃ of logical argon gas, is warming up to 175～250 ℃ again, cooling again behind insulation 15min～1h; The temperature of said cooling can be cooled to 120～160 ℃; The proportioning of said magnetic metal precursor compound, alkylamine, precious metal salt, organic solvent A can be magnetic metal precursor compound: 0.1～1mmol; Alkylamine: 4～20mL; Precious metal salt: 0.005～0.05mmol; Organic solvent A: 0.5～3mL.
In step 3), said organic solvent B can be selected from a kind of in methyl phenyl ethers anisole, benzyl ether, the chloroform etc.; The organic compound that said gold and triphenylphosphine form, the proportioning of organic solvent B can be the organic compound 0.05～1mmol of gold and triphenylphosphine formation; Organic solvent B 0.5～5mL.
In step 4), said cleaning can adopt the mixed liquor of ethanol, hexane and acetone to clean; Said cleaning, the step of centrifugation can repeat 3～5 times; Said drying can adopt vacuum drying.
The present invention is through selecting suitable shell precursor compound for use, and the mode that is aided with injection reaction regulates and control the formation of shell, ensures effective coating of shell, with the nuclear shell type nano meter particle that obtains to have obvious nucleocapsid structure, shell thickness is adjustable.Technical scheme of the present invention is that the precious metal salt with trace is a nucleation accelerating agent; Let the magnetic metal precursor compound in the alkylamine system, reduce earlier in the certain reaction temperature; Generate nano metallic nickel granular material; Inject the organic compound that is dissolved with the gold for preparing in advance fast in suitable temperature then, let the gold that restores be coated on the magnetic metal nuclear that has generated, form nucleocapsid structure.
Nano particle pattern with the present invention obtains is spherical in shape basically, and nucleocapsid structure is obvious, and its particle diameter can be between 20～60nm.Can come to form respectively with single nickel, cobalt with different magnetic metal precursor compounds through change reaction temperature, temperature retention time be nuclear, and the alloy that perhaps forms between iron, cobalt, the nickel three is nuclear, and gold is the nucleocapsid structure of shell.The way at the golden organic compound of proper temperature fast injection that the present invention adopted has been controlled golden reduction rate well, has ensured effective coating of shell.The nuclear shell type nano meter particle of the gold-coating magnetic property metal of preparing has magnetic field capable of using to be reclaimed, separates, and be difficult for advantages such as oxidized simultaneously, so it is applied widely, can be applicable to fields such as catalysis, biology and medical treatment.
Description of drawings
Fig. 1 is the angle of elevation annular dark electromicroscopic photograph that the gold of embodiment 1 preparation coats the nuclear shell type nano meter particle of nickel.In Fig. 1, scale is 30nm, can obviously see, what skin was brighter is gold, and the zone of middle obfuscation is examined corresponding to nickel.
Fig. 2 be the gold of the embodiment 1 preparation nuclear shell type nano meter particle that coats nickel can spectrogram.In Fig. 2, abscissa is energy E nergy (keV), and ordinate is counting rate Counts; The spectrogram of top is to the analysis of nuclear, can find out that the signal of nickel is stronger; Following spectrogram comes from the analysis of shell, can find out the signal that has only gold, and the signal of copper comes from the TEM copper mesh.
Fig. 3 is the transmission electron microscope photo that the gold of embodiment 2 preparations coats the nuclear shell type nano meter particle of nickel.In Fig. 3, scale is 20nm, can find out the light and shade difference that shell and nuclear cause owing to composition is different.
Fig. 4 is the transmission electron microscope photo that the gold of embodiment 3 preparations coats the nuclear shell type nano meter particle of nickel.In Fig. 4, scale is 20nm, can find out the light and shade difference that shell and nuclear cause owing to composition is different.
Fig. 5 is the transmission electron microscope photo that the gold of embodiment 4 preparations coats the nuclear shell type nano meter particle of nickel.In Fig. 5, scale is 20nm, can find out the light and shade difference that shell and nuclear cause owing to composition is different.
Fig. 6 is the transmission electron microscope photo that the gold of embodiment 5 preparations coats the nuclear shell type nano meter particle of nickel.In Fig. 6, scale is 20nm, can find out the light and shade difference that shell and nuclear cause owing to composition is different.
Fig. 7 is the transmission electron microscope photo that the gold of embodiment 6 preparations coats the nuclear shell type nano meter particle of cobalt.In Fig. 7, scale is 10nm, can find out the light and shade difference that shell and nuclear cause owing to composition is different.
Fig. 8 be the gold of the embodiment 6 preparation nuclear shell type nano meter particle that coats cobalt can spectrogram.In Fig. 8, abscissa is energy E nergy (keV), and ordinate is counting rate Counts.The spectrogram of top is to the analysis of nuclear, can find out that the signal of cobalt is stronger; Following spectrogram comes from the analysis of shell, can find out the signal that has only gold, and the signal of copper comes from the TEM copper mesh.
Fig. 9 is the transmission electron microscope photo that the gold of embodiment 7 preparations coats the nuclear shell type nano meter particle of cobalt.In Fig. 9, scale is 5nm, can find out the light and shade difference that shell and nuclear cause owing to composition is different.
Figure 10 is the transmission electron microscope photo that the gold of embodiment 8 preparations coats the nuclear shell type nano meter particle of nickel cobalt (alloy).In Figure 10, scale is 10nm, can find out the light and shade difference that shell and nuclear cause owing to composition is different.
Figure 11 be the gold of the embodiment 8 preparation nuclear shell type nano meter particle that coats nickel cobalt (alloy) can spectrogram.In Figure 11, abscissa is energy E nergy (keV), and ordinate is counting rate Counts.The spectrogram of top is to the analysis of nuclear, can find out that the signal of nickel, cobalt is stronger; Following spectrogram comes from the analysis of shell, can find out the signal that has only gold.The signal of copper comes from the TEM copper mesh.
Figure 12 is the transmission electron microscope photo that the gold of embodiment 9 preparations coats the nuclear shell type nano meter particle of nickel cobalt (alloy).In Figure 12, scale is 5nm, can find out the light and shade difference that shell and nuclear cause owing to composition is different.
Figure 13 be the gold of the embodiment 9 preparation nuclear shell type nano meter particle that coats nickel cobalt (alloy) can spectrogram.In Figure 13, abscissa is energy E nergy (keV), and ordinate is counting rate Counts.The spectrogram of top is to the analysis of nuclear, can find out that the signal of nickel, cobalt is stronger; Following spectrogram comes from the analysis of shell, can find out the signal that has only gold.The signal of copper comes from the TEM copper mesh.
Figure 14 is the transmission electron microscope photo that the gold of embodiment 10 preparations coats the nuclear shell type nano meter particle of nickel cobalt (alloy).In Figure 14, scale is 5nm, can find out the light and shade difference that shell and nuclear cause owing to composition is different.
Figure 15 be the gold of the embodiment 10 preparation nuclear shell type nano meter particle that coats nickel cobalt (alloy) can spectrogram.In Figure 15, abscissa is energy E nergy (keV), and ordinate is counting rate Counts.The spectrogram of top is to the analysis of nuclear, can find out that the signal of nickel, cobalt is stronger; Following spectrogram comes from the analysis of shell, can find out the signal that has only gold.The signal of copper comes from the TEM copper mesh.
The specific embodiment
Embodiment 1
0.5mmol nickel acetylacetonate, 6ml oleyl amine are added in the there-necked flask; Under the protection of argon gas, mix, the mixed liquor with 0.012mmol gold chloride, 0.3ml methyl phenyl ethers anisole adds in the there-necked flask again, is warming up to 50 ℃ behind the stirring 10min; Insulation 10min; Be warming up to 200 ℃ then, insulation 20min is cooled to 150 ℃ then.The organic compound of the gold that quick injection 0.5mmol prepares in advance and the mixture of 2ml chloroform, cooling naturally behind 140 ℃ of insulation 30min adds acetone nano particle is precipitated; Through centrifugal taking-up reaction mother liquor; Use ethanol, acetone, n-hexane mixed solution cyclic washing then, centrifugal three times, last vacuum drying; Obtain the powder product, its Electronic Speculum figure is as depicted in figs. 1 and 2 respectively with the ability spectrogram.
0.5mmol nickel acetylacetonate, 6ml oleyl amine are added in the there-necked flask; Under the protection of argon gas, mix, the mixed liquor with 0.012mmol gold chloride, 0.3ml ethanol adds in the there-necked flask again, is warming up to 50 ℃ behind the stirring 10min; Insulation 10min; Be warming up to 200 ℃ then, insulation 20min is cooled to 150 ℃ then.The organic compound of the gold that quick injection 0.5mmol prepares in advance and the mixture of 2ml chloroform, cooling naturally behind 130 ℃ of insulation 30min adds acetone nano particle is precipitated; Through centrifugal taking-up reaction mother liquor, use ethanol, acetone, n-hexane mixed solution cyclic washing then, centrifugal 3 times; Last vacuum drying; Obtain the powder product, figure is as shown in Figure 3 for its Electronic Speculum, and its ability spectrogram and Fig. 2 are similar.
Embodiment 3
0.5mmol nickel acetylacetonate, 5ml oleyl amine, 2ml lauryl amine are added in the there-necked flask; Under the protection of argon gas, mix, the mixed liquor with 0.012mmol gold chloride, 0.3ml toluene adds in the there-necked flask again, is warming up to 50 ℃ behind the stirring 10min; Insulation 10min; Be warming up to 210 ℃ then, insulation 20min is cooled to 150 ℃ then.The organic compound of the gold that quick injection 0.3mmol prepares in advance and the mixture of 3ml chloroform, cooling naturally behind 130 ℃ of insulation 30min adds acetone nano particle is precipitated; Through centrifugal taking-up reaction mother liquor, use ethanol, acetone, n-hexane mixed solution cyclic washing then, centrifugal three times; Last vacuum drying; Obtain the powder product, figure is as shown in Figure 4 for its Electronic Speculum, and its ability spectrogram and Fig. 2 are similar.
0.5mmol nickel acetylacetonate, 6ml oleyl amine are added in the there-necked flask; Under the protection of argon gas, mix, the mixed liquor with 0.01mmol silver nitrate, 0.3ml two Bian ethers adds in the there-necked flask again, is warming up to 50 ℃ behind the stirring 10min; Insulation 10min; Be warming up to 220 ℃ then, insulation 20min is cooled to 150 ℃ then.The organic compound of the gold that quick injection 0.5mmol prepares in advance and the mixture of 3ml methyl phenyl ethers anisole, cooling naturally behind 140 ℃ of insulation 30min adds acetone nano particle is precipitated; Through centrifugal taking-up reaction mother liquor, use ethanol then, acetone; N-hexane mixed solution cyclic washing, centrifugal three times, last vacuum drying; Obtain the powder product, figure is as shown in Figure 5 for its Electronic Speculum, and its ability spectrogram and Fig. 2 are similar.
Embodiment 5
0.5mmol nickel acetate, 6ml oleyl amine are added in the there-necked flask; Under the protection of argon gas, mix, the mixed liquor with 0.01mmol silver nitrate, 0.3ml methyl phenyl ethers anisole adds in the there-necked flask again, is warming up to 50 ℃ behind the stirring 10min; Insulation 10min; Be warming up to 195 ℃ then, insulation 20min is cooled to 160 ℃ then.The organic compound of the gold that quick injection 0.5mmol prepares in advance and the mixture of 3ml chloroform, cooling naturally behind 135 ℃ of insulation 30min adds acetone nano particle is precipitated; Through centrifugal taking-up reaction mother liquor, use ethanol then, acetone; N-hexane mixed solution cyclic washing, centrifugal three times, last vacuum drying; Obtain the powder product, figure is as shown in Figure 6 for its Electronic Speculum, and its ability spectrogram and Fig. 2 are similar.
0.5mmol acetylacetone cobalt, 6ml oleyl amine are added in the there-necked flask; Under the protection of argon gas, mix, the mixed liquor with 0.012mmol gold chloride, 0.3ml methyl phenyl ethers anisole adds in the there-necked flask again, is warming up to 50 ℃ behind the stirring 10min; Insulation 10min; Be warming up to 230 ℃ then, insulation 20min is cooled to 150 ℃ then.The organic compound of the gold that quick injection 0.5mmol prepares in advance and the mixture of 2ml methyl phenyl ethers anisole, cooling naturally behind 140 ℃ of insulation 30min adds acetone nano particle is precipitated; Through centrifugal taking-up reaction mother liquor, use ethanol then, acetone; N-hexane mixed solution cyclic washing, centrifugal three times, last vacuum drying; Obtain the powder product, its Electronic Speculum figure and ability spectrogram are respectively like Fig. 7 and shown in Figure 8.
Embodiment 7
0.5mmol acetylacetone cobalt, 6ml oleyl amine are added in the there-necked flask; Under the protection of argon gas, mix, the mixed liquor with 0.012mmol gold chloride, 0.3ml methyl phenyl ethers anisole adds in the there-necked flask again, is warming up to 50 ℃ behind the stirring 10min; Insulation 10min; Be warming up to 230 ℃ then, insulation 20min is cooled to 150 ℃ then.The organic compound of the gold that quick injection 0.5mmol prepares in advance and the mixture of 3ml chloroform, cooling naturally behind 120 ℃ of insulation 30min adds acetone nano particle is precipitated; Through centrifugal taking-up reaction mother liquor, use ethanol then, acetone; N-hexane mixed solution cyclic washing, centrifugal three times, last vacuum drying; Obtain the powder product, figure is as shown in Figure 9 for its Electronic Speculum, and its ability spectrogram and Fig. 8 are similar.
0.3mmol nickel acetylacetonate, 0.2mmol acetylacetone cobalt, 6ml oleyl amine are added in the there-necked flask; Under the protection of argon gas, mix, the mixed liquor with 0.012mmol gold chloride, 0.3ml methyl phenyl ethers anisole adds in the there-necked flask again, is warming up to 50 ℃ behind the stirring 10min; Insulation 10min; Be warming up to 220 ℃ then, insulation 30min is cooled to 145 ℃ then.The organic compound of the gold that quick injection 0.5mmol prepares in advance and the mixture of 2ml methyl phenyl ethers anisole, cooling naturally behind 140 ℃ of insulation 30min adds acetone nano particle is precipitated; Through centrifugal taking-up reaction mother liquor, use ethanol then, acetone; N-hexane mixed solution cyclic washing, centrifugal three times, last vacuum drying; Obtain the powder product, its Electronic Speculum figure and ability spectrogram are respectively like Figure 10 and shown in Figure 11.
Embodiment 9
0.3mmol nickel acetylacetonate, 0.2mmol cobalt acetate, 6ml oleyl amine are added in the there-necked flask; Under the protection of argon gas, mix, the mixed liquor with 0.012mmol gold chloride, 0.3ml methyl phenyl ethers anisole adds in the there-necked flask again, is warming up to 50 ℃ behind the stirring 10min; Insulation 10min; Be warming up to 210 ℃ then, insulation 30min is cooled to 150 ℃ then.The organic compound of the gold that quick injection 0.5mmol prepares in advance and the mixture of 2ml methyl phenyl ethers anisole, cooling naturally behind 140 ℃ of insulation 30min adds acetone nano particle is precipitated; Through centrifugal taking-up reaction mother liquor, use ethanol then, acetone; N-hexane mixed solution cyclic washing, centrifugal three times, last vacuum drying; Obtain the powder product, its Electronic Speculum figure and ability spectrogram are respectively like Figure 12 and shown in Figure 13.
0.4mmol nickel acetate, 0.1mmol cobalt acetate, 6ml oleyl amine are added in the there-necked flask; Under the protection of argon gas, mix, the mixed liquor with 0.012mmol gold chloride, 0.3ml methyl phenyl ethers anisole adds in the there-necked flask again, is warming up to 50 ℃ behind the stirring 10min; Insulation 10min; Be warming up to 195 ℃ then, insulation 30min is cooled to 150 ℃ then.The organic compound of the gold that quick injection 0.5mmol prepares in advance and the mixture of 2ml methyl phenyl ethers anisole, cooling naturally behind 140 ℃ of insulation 30min adds acetone nano particle is precipitated; Through centrifugal taking-up reaction mother liquor, use ethanol then, acetone; N-hexane mixed solution cyclic washing, centrifugal three times, last vacuum drying; Obtain the powder product, its Electronic Speculum figure and ability spectrogram are respectively like Figure 14 and shown in Figure 15.
Claims (10)
1. magnetic metal-gold core-shell type nanometer particle process method is characterized in that may further comprise the steps:
1) 1g gold chloride and 1.36g triphenylphosphine are dissolved in respectively in 50mL and the 35mL ethanol, again product are filtered, cleans, dries, the organic compound that De Jin and triphenylphosphine form;
2) the magnetic metal precursor compound is mixed with alkylamine, get mixed liquor A, precious metal salt is mixed with organic solvent A again, after the temperature reaction of adding mixed liquor A, cooling gets nano metallic nickel granular material;
3) organic compound with resulting gold of step 1) and triphenylphosphine formation is dissolved in the organic solvent B; Implantation step 2) resulting nano metallic nickel granular material; Be incubated 20min～1h down at 120～160 ℃; Gold will be reduced out and be coated on the established nano metallic nickel granular material, obtain being the nano particle of gold and magnetic metal nucleocapsid structure;
4) nano particle that is gold and magnetic metal nucleocapsid structure with the step 3) gained cleans, centrifugation, and drying gets the powder product, magnetic metal-gold core-shell type nano particle.
2. a kind of magnetic metal as claimed in claim 1-gold core-shell type nanometer particle process method; It is characterized in that in step 2) in, the said magnetic metal precursor compound is mixed with alkylamine is under the protection of inert gas, the magnetic metal precursor compound to be mixed with alkylamine.
3. a kind of magnetic metal as claimed in claim 1-gold core-shell type nanometer particle process method is characterized in that in step 2) in, at least a in the acetylacetonate compound of said magnetic metal precursor compound chosen from Fe, cobalt, nickel or the acetate.
4. a kind of magnetic metal as claimed in claim 1-gold core-shell type nanometer particle process method is characterized in that in step 2) in, said alkylamine is selected from a kind of in oleyl amine, lauryl amine, the cetylamine.
5. a kind of magnetic metal as claimed in claim 1-gold core-shell type nanometer particle process method is characterized in that in step 2) in, said precious metal salt is selected from gold chloride or silver nitrate.
6. a kind of magnetic metal as claimed in claim 1-gold core-shell type nanometer particle process method is characterized in that in step 2) in, said organic solvent A is selected from a kind of in methyl phenyl ethers anisole, ethanol, the toluene.
7. a kind of magnetic metal as claimed in claim 1-gold core-shell type nanometer particle process method; It is characterized in that in step 2) in; The condition of said adding mixed liquor A temperature reaction; Be to stir 5～30min, be warming up to 175～250 ℃ again, cooling again behind insulation 15min～1h at 50～90 ℃ of logical argon gas; The temperature of said cooling is to be cooled to 120～160 ℃.
8. a kind of magnetic metal as claimed in claim 1-gold core-shell type nanometer particle process method; It is characterized in that in step 2) in, the proportioning of said magnetic metal precursor compound, alkylamine, precious metal salt, organic solvent A is magnetic metal precursor compound: 0.1～1mmol; Alkylamine: 4～20mL; Precious metal salt: 0.005～0.05mmol; Organic solvent A: 0.5～3mL.
9. a kind of magnetic metal as claimed in claim 1-gold core-shell type nanometer particle process method is characterized in that in step 3), and said organic solvent B is selected from a kind of in methyl phenyl ethers anisole, benzyl ether, the chloroform; The organic compound that said gold and triphenylphosphine form, the proportioning of organic solvent B are preferably the organic compound 0.05～1mmol of gold and triphenylphosphine formation; Organic solvent B 0.5～5mL.
10. a kind of magnetic metal as claimed in claim 1-gold core-shell type nanometer particle process method is characterized in that in step 4), and said cleaning is to adopt the mixed liquor of ethanol, hexane and acetone to clean; Said cleaning, the step of centrifugation preferably repeat 3～5 times; The said dry vacuum drying of adopting.
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| CN103769605A (en) * | 2014-02-13 | 2014-05-07 | 厦门大学 | Method for synthesizing oil-soluble gold nanoparticles |
| CN105405975A (en) * | 2015-11-18 | 2016-03-16 | 苏州大学 | Cu@Cu-Au nano-particle with core-shell structure and preparation method and application thereof |
| CN105405975B (en) * | 2015-11-18 | 2017-09-22 | 苏州大学 | Cu@Cu Au nano particles with core shell structure and its preparation method and application |
| CN105499599A (en) * | 2015-12-15 | 2016-04-20 | 安徽大学 | Preparation method for small-size gold nano-clusters, and gold nano-clusters |
| CN107030295A (en) * | 2017-03-24 | 2017-08-11 | 同济大学 | A kind of preparation method of magnetic/gold nanocomposite particle |
| CN109261981A (en) * | 2018-08-20 | 2019-01-25 | 浙江师范大学 | Bimetallic cobalt-based core-shell material and the preparation method and application thereof |
| CN109261981B (en) * | 2018-08-20 | 2022-02-15 | 浙江师范大学 | Bimetal cobalt-based core-shell material and preparation method and application thereof |
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