CN102094246A - Gold nucleus and silver shell double-metal nanocrystal and preparation method thereof - Google Patents
Gold nucleus and silver shell double-metal nanocrystal and preparation method thereof Download PDFInfo
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- CN102094246A CN102094246A CN2009102424252A CN200910242425A CN102094246A CN 102094246 A CN102094246 A CN 102094246A CN 2009102424252 A CN2009102424252 A CN 2009102424252A CN 200910242425 A CN200910242425 A CN 200910242425A CN 102094246 A CN102094246 A CN 102094246A
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Abstract
The invention relates to a gold nucleus and silver shell double-metal nanocrystal and a preparation method thereof. The crystal is in a rod-shaped structure with a regular crystalline form, wherein the rod-shaped structure is focused on a {100} surface and comprises a double-cube triangle, a cube and a five-twin crystal section, and simultaneously the side surface of the rod-shaped structure is a {100} type crystal surface. The preparation method comprises the following steps of: heating a polyhydroxy-alcohol solution containing chloroauric acid, polyvinylpyrrolidone and silver nitrate, cooling at a room temperature and carrying out centrifugal precipitation to obtain a gold crystal seed; and adding the gold crystal seed obtained by centrifugal separation to a polyhydroxy-alcohol solution containing the polyvinylpyrrolidone, adding the silver nitrate in a molar ratio [AgNO3]/[HuAuCl4], heating by using an oil bath to obtain a product solution, and then carrying out centrifugation to obtain a product. In the first step of reaction in the preparation method, a certain trace of silver nitrate is added to the solution so that the shape of a gold nucleus is effectively controlled, the crystal with a regular crystalline form is obtained, and the shape of a silver shell is finally decided on the shape of the gold seed. The preparation method realizes rapid and batch controllable preparation of a silver-coated gold nano nucleus/silver structure crystal forced on the {100} surface.
Description
Technical field
The present invention relates to a kind of nanocrystal and preparation method, particularly a kind of controllable shapes so that { gold of 100} type crystal face is examined the preparation method of nanocrystal and this nanocrystal of silver-colored shell structure with nucleocapsid structure.
Background technology
Different with the single-component metal nanoparticle, the bimetal nano particle enjoys investigator's concern because of its unique optics, electricity, catalysis and magnetic performance.Because above-mentioned characteristic depends primarily on composition, the size and dimension of nanoparticle, so controllably prepare the research focus that the bimetal nano particle with different structure and composition just becomes people.Bimetal nano crystal with core/shell structure is exactly a typical example.Precious Metals-Gold (Au) has identical face-centered cubic crystal structure with silver (Ag), and (Au (0.408nm), Ag (0.409nm)) is very close for their lattice parameter, thereby can form the gold core/silver shell nanostructure of multiple alloy and silver coating gold nuclear.Gold core/silver shell bimetal nano structured material is with optics, the electrology characteristic of stratum nucleare and shell material and the monopolizing characteristic that is different from single component.
People have invented many methods that are used for synthesizing the bimetal nano particle.For example, ethanol-Citrate trianion reduction method (Link, S.; Wang, Z.L.; E1-Sayed, M.A.J.Phys.Chem.B 1999,103, and 3529); Microemulsion method of reducing (Chen Dong-Hwang and Chen Cheng-Jia J.Mater.Chem., 2002,12,1557) etc.Wherein, the polyalcohols reduction method is a kind of novel method of synthetic bimetal nano particle.This method mainly is to select proper polymer as stablizer, and the reduction process by polyhydroxy-alcohol (as: ethylene glycol (EG), 1,4-butyleneglycol, 1,5-pentanediol (PD), tetraethylene-glycol etc.) prepares noble metal nano particles.Polyhydroxy-alcohol not only can more easily dissolve various presoma salt as solvent, and the high boiling point that they had can fully guarantee precious metal salt under hot conditions, promptly is reduced to metal simple-substance.In this process, the adding of high molecular polymer such as polyvinylpyrrolidone (PVP) can be used to regulate and control the nucleation and the process of growth of noble metal nano particles.2006, we once found to use nitrogen, and nitrogen-dimethyl formamide (DMF) is made solvent, and in the presence of tensio-active agent polyvinylpyrrolidone (PVP), oil bath adds thermal reduction Silver Nitrate (AgNO
3), can make high yield that { 111} type crystal face is main silver nano-grain.(Gao，Y.；Jiang，P.et.al.J.Cryst.Growth2006，289，376)。But silver coats the synthetic method of the controllable shapes of the golden gold core/silver core/shell nanoparticles of examining and still remains to be studied.
Summary of the invention
The objective of the invention is to: it is uncontrollable that (1) overcomes the bimetal nano growth shape that in the past has the preparation core/shell structure, and { the 100} crystal face is the technical deficiency that main silver coats the gold/galactic nucleus shell nanostructure of golden nuclear in particularly preparation; Thereby a kind of utilization polyalcohols reduction reaction is provided, as solvent and reductive agent, and in solution, adds the Silver Nitrate (AgNO of certain micro-concentrations with the higher polyhydroxy-alcohol of boiling point
3), controlling the one-tenth nuclear shape of gold nuclear, thus realize controllably synthetic have specified shape { the 100} crystal face is that main silver coats gold bimetal nano crystalline preparation method nuclear, that have gold/galactic nucleus shell nanostructure.
Another object of the present invention is to, obtain a kind of so that { silver of 100} crystal face coats the gold/galactic nucleus shell bimetal nano crystal of gold nuclear by preparation method of the present invention, this nanocrystal has polyhedral structure, can also can be used as efficient selective catalyzer and nano-disinfection, virus killing drug as the building material of high-sensitivity biological sensor.
The object of the present invention is achieved like this:
A kind of gold nuclear provided by the invention and silver-colored shell bimetal nano crystal, it is characterized in that, have the crystalline form rule, based on { gold of 100} face nuclear and silver-colored shell bimetal nano crystal, this crystalline form comprises two cube triangle, regular cubes and has while side, five heavy twin cross sections for { club shaped structure of 100} type crystal face, configuration diagram are seen accompanying drawing 1.
Gold nuclear of the present invention has nucleocapsid structure with silver-colored shell bimetal nano crystal, with optics, the electrology characteristic of two kinds of composition materials.Precious Metals-Gold (Au) has identical face-centered cubic crystal structure with silver (Ag), and (Au (0.408nm), Ag (0.409nm)) is very close for their lattice parameter, thereby can form multiple alloy and silver and coat the golden gold of examining and examine silver-colored shell nanostructure.The silver that is obtained coats the information of gold core/silver shell crystal morphology and configuration aspects can pass through field emission scanning electron microscope (FE-SEM) and the acquisition of transmission electron microscope (TEM) sign; The information of crystalline structure aspect also can be passed through X-ray diffraction (XRD) and characterize acquisition; The information of plane of crystal chemical state aspect can be passed through x-ray photoelectron spectroscopy (XPS) and characterize acquisition.
A kind of gold nuclear provided by the invention and silver-colored shell bimetal nano crystalline preparation method as solvent and reductive agent, and add certain density Silver Nitrate (AgNO with the higher polyhydroxy-alcohol of boiling point in solution
3), may further comprise the steps:
1) preparation gold nuclear stoste:
Compound concentration is the hydrochloro-auric acid (HAuCl of 0.05M-1M
44H
2O) and concentration be the polyhydroxy-alcohol solution of 1M-10M polyvinylpyrrolidone (PVP);
2) the silver-colored shell stoste of preparation:
Compound concentration is the PVP of 1M-10M and the Silver Nitrate (AgNO that concentration is 0.1mM-1M
3) polyhydroxy-alcohol solution;
3) preparation reactant mixing solutions:
3-1) the 0.05M-1M HAuCl for preparing according to step 1)
44H
2The polyhydroxy-alcohol solution of the 1M-10M polyvinylpyrrolidone of O and step 1) preparation, by hydrochloro-auric acid: the polyvinylpyrrolidone mol ratio is 1: 1-10, the mutual thorough mixing in hydrochloro-auric acid/Silver Nitrate mol ratio=500/1 obtain reactant mixing solutions 1;
3-2) get 0.1M-1M Silver Nitrate and 1M-10M polyvinylpyrrolidonesolution solution, by [AgNO
3]: the polyvinylpyrrolidone mol ratio is 1: the mutual thorough mixing of 1-10 obtains reactant mixing solutions 2; Wherein, described AgNO
3With respect to the mol ratio of hydrochloro-auric acid in the 1-20 scope;
4) nanocrystal of the silver-colored shell structure of synthetic gold nuclear:
4-1) with step 3-1) gained preparation gold nuclear stoste (reactant mixing solutions 1) is heated to boiling state in oil bath, kept 1-2 hour, again mixed solution naturally cooled to room temperature; It is centrifugal to take out the back, after supernatant liquor is separated, obtains Jin Jing and plants precipitation;
4-2) get above-mentioned steps 4-1) gained Jin Jing plants precipitation, joins step 2) in the preparation silver shell stoste (reactant mixing solutions 2) prepared, oil bath is heated to the solution boiling, keeps obtaining product solution more than 2 hours; Centrifugal then 10-30 minute, remove supernatant liquor, collecting precipitation thing and with deionized water (10-50mL) repetitive scrubbing precipitation obtains having based on { the gold nuclear and the silver-colored shell bimetal nano crystal of 100} face after centrifugal.
In above-mentioned technical scheme, described polyhydroxy-alcohol comprises: ethylene glycol (EG), 1,4-butyleneglycol, 1,5-pentanediol (PD) or tetraethylene-glycol.
In above-mentioned technical scheme, described step 4-1) centrifugal rotational speed in is 3000rpm-6000rpm, centrifugal 10-30 minute.
In above-mentioned technical scheme, described step 4-2) centrifugal rotational speed in is 10000rpm-15000rpm, keeps 10-30 minute.
In above-mentioned technical scheme, described step 4-2) the deionized water wash consumption is 10-50mL in.
Preparation silver provided by the invention coats gold core/silver shell nanometer material method, and the gold of the controllable shapes that it prepares is examined and silver coats the structural analysis of gold core/silver core/shell nanoparticles and it is as follows to form mechanism:
A) crystalline structure of gold nuclear and formation mechanism thereof
Heating contains the hydrochloro-auric acid polyhydroxy-alcohol solution of a small amount of Silver Nitrate, and can obtain monocrystalline octahedron, cubic monocrystalline body, twin ditrigon, the two hexagons of twin, cross section is pentagonal five heavy twins rod nm gold particless (seeing accompanying drawing 2a, Fig. 2 b, Fig. 2 c, Fig. 2 d, Fig. 2 e).Usually at the crystalline nucleation stage, the appearance of cenotype needs consumes energy.When the size of gold nuclear surpassed the critical nucleation size, gold nuclear could exist.After the nucleation, new gold atom can add gold nuclear to and go up the continued growth of feasible gold nuclear.This process can release energy.In such stage, kinetic factor is determining the growth and the structure of gold nuclear.Yet the shape of the final gold nano grain that forms and structure are by the shape of the initial gold nuclear that forms and structures shape.When gold nuclear was small-sized, conversion can take place in the structure of gold nuclear between monocrystalline and twin structure.Particle is more little, changes fast more.For gold, when particle was very little, because the thermodynamics factor, the probability that the twin structure gold nano grain occurs was far longer than the probability that single crystal structure occurs, so the shape of final resulting gold nano grain and structure are not single.
B) silver coats the gold nano grain shape and forms mechanism
Planting with difform Jin Jing is nuclear, prepared silver coats gold nuclear/core-shell nanoparticles and has multiple shape, comprises cubes, two cubes of triangles and have five heavy twin cross sections being the { club shaped structure of 100} type crystal face (seeing accompanying drawing 3a, Fig. 3 b, Fig. 3 c, Fig. 3 d) in the side simultaneously.
The different crystal face of face-centered cubic crystal has different surface energies, and for low index crystal face, surface energy is γ in proper order
(111)＜γ
(100)＜γ
(110)According to the Wulff rule, under the thermodynamic(al)equilibrium condition, the face-centered cubic nanocrystal is mainly by { 111} and { 100} class profile formation.The crystal that is the face-centered cubic type can be by low energy { 111} and { 100} class profile constitutes various polyhedral structures.Yet because the complicacy of crystal growing process in the solution, kinetic factor is dominant sometimes.Generally speaking, the speed of growth is the crystal face easily dissolved faster, and the slower crystal face of the speed of growth finally can remain.Along the speed of growth of different crystal plane direction than the shape that has determined products therefrom.The gold nano crystal seed generally is by { some shapes that the 111} crystal face constitutes comprise ditrigon, two hexagon, octahedron, decahedron etc.Yet, along with a small amount of Silver Nitrate (AgNO in the polyhydroxy-alcohol solution that contains PVP
3) existence, { the cubes golden nanometer particle that the 100} crystal face constitutes can appear in the product.
The kinetics of adsorption of silver ions and the difference of PVP tensio-active agent adsorption strength on different crystal faces will cause the variation of different components particle surface crystal face.Since the PVP active agent molecule would rather be adsorbed on gold 111} crystal face and silver the 100} crystal face, thus can passivation these crystal faces, thereby it is remained.
Formation mechanism analysis by gold nuclear and silver being coated golden core-shell nano as can be known, preparation method of the present invention can control and obtain that { the 100} face is the shape that main silver coats gold core/silver shell nanostructure.
The invention has the advantages that:
1. the present invention preparation so that { the bimetal nano crystal of the gold core/silver core/shell nanoparticles of 100} crystal face has optics, the electrology characteristic of two kinds of composition materials.This crystal has the crystalline form rule, comprises two cube triangle, regular cubes and has five heavy contractions side of brilliant cross section while for { club shaped structure of 100} type crystal face, configuration diagram are seen accompanying drawing 1a, Fig. 1 b, Fig. 1 c, Fig. 1 d, Fig. 1 e.The silver that is obtained coats the information of gold core/silver shell crystal morphology and configuration aspects can pass through field emission scanning electron microscope (FE-SEM) and the acquisition of transmission electron microscope (TEM) sign; The information of crystalline structure aspect also can be passed through X-ray diffraction (XRD) and characterize acquisition; The information of plane of crystal chemical state aspect can be passed through x-ray photoelectron spectroscopy (XPS) and characterize acquisition.
The present invention preparation { the 100} crystal face is that main silver coats gold nuclear/core-shell nanoparticles, can also can be used as efficient selective catalyzer and nano-disinfection, virus killing drug as the building material of high-sensitivity biological sensor.
The present invention preparation based on the bimetal nano crystalline method of the gold core/silver core/shell nanoparticles of 100} crystal face owing to adopt the higher polyhydroxy-alcohol of boiling point as solvent and reductive agent, and in solution a spot of AgNO of adding
3Be the auxiliary polyalcohols reduction reaction of polyvinylpyrrolidone (PVP) of additive, so controllably synthetic bimetal nano crystal with gold/galactic nucleus shell nanostructure of specific { 100} type silver coating crystal face, the crystalline form rule gold nuclear.
4. the equipment that preparation method of the present invention uses all is routinize construction equipment, safety, versatility, workable; The technological process of production is simple, and can accomplish scale production.
Description of drawings
Fig. 1 a be method of the present invention preparation so that { gold of 100} crystal face is examined and is the structural representation of octahedral cubes gold core/silver shell bimetal nano crystal grain.
Fig. 1 b be the inventive method preparation so that { gold of 100} crystal face is examined and is the structural representation of cubical cubes gold core/silver shell duplex metal nano granule.
Fig. 1 c be the inventive method preparation so that { the gold nuclear of 100} crystal face is the structural representation of two cube corner gold core/silver shell duplex metal nano granules of pair triangles.
Fig. 1 d be the inventive method preparation so that { the gold nuclear of 100} crystal face is the structural representation of pair hexagonal pair of cube corner gold core/silver shell duplex metal nano granules.
Fig. 1 e be the inventive method preparation so that { it is that cross section is that the cross section of pentagon club shaped structure is the structural representation of the gold core/silver shell duplex metal nano granule of pentagon club shaped structure that the gold of 100} crystal face is examined.
Fig. 2 a is the scanning electron microscope image that the octahedra Jin Jing of monocrystalline plants.
Fig. 2 b is the scanning electron microscope image of the cubic monocrystalline body gold seed nuclei of the inventive method preparation.
Fig. 2 c is the scanning electron microscope image of the two triangle gold of the twin of the inventive method preparation seed nuclei.
Fig. 2 d is the scanning electron microscope image of the two hexagon gold of the twin of the inventive method preparation seed nuclei.
Fig. 2 e is the scanning electron microscope image of the bar-shaped golden seed nuclei of five heavy twins of the inventive method preparation.
Fig. 3 a is that planting with the octahedra Jin Jing of monocrystalline of the inventive method preparation is the transmission electron microscope image of examining the bimetal nuclear/shell nanostructure of the cubes silver shell for preparing.
Fig. 3 b is that planting with cubic monocrystalline body Jin Jing of the inventive method preparation is the transmission electron microscope image of examining the bimetal nuclear/shell nanostructure of the cubes silver shell for preparing.
Fig. 3 c is that planting with the two triangle Jin Jings of twin of the inventive method preparation is the transmission electron microscope image of examining the bimetal nuclear/shell nanostructure of cube two three horn silver AgX shells that prepare.
Fig. 3 d is that planting with the two hexagon Jin Jings of twin of the inventive method preparation is the transmission electron microscope image of examining the bimetal nuclear/shell nanostructure of cube two three horn silver AgX shells that prepare.
Fig. 3 e is that planting with the bar-shaped Jin Jing of five heavy twins of the inventive method preparation is the transmission electron microscope image that five of nuclear preparation weighs the bar-shaped bimetal nuclear/shell nanostructure of twins.
Embodiment
Describe the present invention below in conjunction with the drawings and specific embodiments, but not as a limitation of the invention.
Embodiment 1
Present embodiment is by utilizing 1,5-pentanediol (PD) is as solvent and reductive agent, preparation has difform gold/galactic nucleus shell structure, the gold nuclear and the silver-colored shell bimetal nano crystal shape of present embodiment preparation, this bimetal nano crystal have the crystalline form rule, so that { gold of 100} face nuclear and silver-colored shell bimetal nano crystal, this crystalline form comprise cubes (seeing accompanying drawing 3a and 3b), two cubes of triangles (seeing accompanying drawing 3c and 3d) and have five heavy twin cross sections and is { the club shaped structure of 100} type crystal face (seeing accompanying drawing 3e) etc. in the side simultaneously.
The gold nuclear and the concrete preparation method of silver-colored shell bimetal nano crystalline of present embodiment may further comprise the steps:
1) with 0.05M hydrochloro-auric acid (HAuCl
43H
2O) 1,1 of 5-pentanediol (PD) solution 3 milliliters (mL) and 0.15M polyvinylpyrrolidone (PVP), 3 milliliters of (mL) mutual thorough mixing of 5-pentanediol (PD) solution, then, with 1 of 0.1mM Silver Nitrate, 5-pentanediol (PD) solution 3 milliliters (mL) splashes in the above-mentioned mixed solution, obtains reactant mixing solutions 1;
2) preparation contains 0.9M PVP and 0.3M Silver Nitrate (AgNO
3) 1,5-pentanediol (PD) solution 9ml obtains reactant mixing solutions 2;
3) with step 1) gained reaction mixture 1 heating 1-2h, the products therefrom mixed solution is naturally cooled to room temperature; Afterwards, centrifugation 10 minutes, centrifugal rotational speed is 5000rpm or 6000rpm for example, after the separation of supernatant, obtains Jin Jing and plants precipitation;
4) get the resulting Jin Jing's kind of step 3), join step 2) in the gained reactant mixing solutions 2, oil bath is heated to the boiling of PD solution, obtains product solution after the PD boiling point keeps 3 hours; Centrifugal then 20 minutes, centrifugal rotational speed for example was 13000rpm, 15000rpm or 16000rpm, removed supernatant liquor, the collecting precipitation thing, and throw out and with deionized water (10-50mL) repetitive scrubbing precipitation obtains the nanocrystal of gold nuclear and silver-colored shell structure after centrifugal.
Embodiment 2
Present embodiment is by utilizing 1, and the 4-butyleneglycol is as solvent and reductive agent, and preparation has difform gold/galactic nucleus shell structure.These shapes comprise cubes (accompanying drawing 3a and 3b), cube two triangles (accompanying drawing 3c and 3d) and have while side, five heavy twin cross sections is the { club shaped structure of 100} type crystal face (accompanying drawing 3e) etc.
Concrete preparation method may further comprise the steps:
1) with 0.05M hydrochloro-auric acid (HAuCl
43H
2O) 1,1 of 4-butanediol solution 10 milliliters (mL) and 0.15M polyvinylpyrrolidone (PVP), 4-butanediol solution 10 milliliters (mL) is thorough mixing mutually, then, with 1 of 0.1mM Silver Nitrate, 4-butanediol solution 10 milliliters (mL) splashes in the above-mentioned mixed solution, obtains reactant mixing solutions 1;
2) preparation contains 0.9M PVP and 0.3M Silver Nitrate (AgNO
3) 1,4-butanediol solution 30ml obtains reactant mixing solutions 2;
3) with step 1) gained reaction mixture 1 heating 1-2h, the products therefrom mixed solution is naturally cooled to room temperature; Afterwards, centrifugal (5000rpm) 10 minutes after the separation of supernatant, obtains Jin Jing and plants precipitation;
4) get the resulting Jin Jing's kind of step 3), join step 2) in the gained reactant mixing solutions 2, oil bath is heated to 1, the boiling of 4-butanediol solution, 1,4-butyleneglycol boiling point keeps obtaining product solution after 3 hours; Centrifugal then (13000rpm) 20 minutes removes supernatant liquor, and collecting precipitation thing and with deionized water (10-50mL) repetitive scrubbing precipitation obtains the nanocrystal of gold nuclear and silver-colored shell structure after centrifugal.
Embodiment 3
Present embodiment is by utilizing ethylene glycol (EG) as solvent and reductive agent, and preparation has difform gold/galactic nucleus shell structure.These shapes comprise cubes (accompanying drawing 3a and 3b), cube two triangles (accompanying drawing 3c and 3d) and have while side, five heavy twin cross sections is the { club shaped structure of 100} type crystal face (accompanying drawing 3e) etc.
Concrete preparation method may further comprise the steps:
1) with 0.05M hydrochloro-auric acid (HAuCl
43H
2Ethylene glycol (EG) solution of ethylene glycol O) (EG) solution 20 milliliters (mL) and 0.15M polyvinylpyrrolidone (PVP) 20 milliliters (mL) is thorough mixing mutually, then, ethylene glycol (EG) solution 20 milliliters (mL) of 0.1mM Silver Nitrate is splashed in the above-mentioned mixed solution, obtain reactant mixing solutions 1;
2) preparation contains 0.9M PVP and 0.3M Silver Nitrate (AgNO
3) ethylene glycol (EG) solution 60ml, obtain reactant mixing solutions 2;
3) with step 1) gained reaction mixture 1 heating 1-2h, the products therefrom mixed solution is naturally cooled to room temperature; Afterwards, centrifugal (5000rpm) 10 minutes after the separation of supernatant, obtains Jin Jing and plants precipitation;
4) get the resulting Jin Jing's kind of step 3), join step 2) in the gained reactant mixing solutions 2, oil bath is heated to the boiling of ethylene glycol (EG) solution, obtains product solution after ethylene glycol (EG) boiling point keeps 3 hours; Centrifugal then (13000rpm) 20 minutes removes supernatant liquor, and collecting precipitation thing and with deionized water (10-50mL) repetitive scrubbing precipitation obtains the nanocrystal of gold nuclear and silver-colored shell structure after centrifugal.
Certainly; the present invention also can have other various embodiments; under the situation that does not deviate from spirit of the present invention and essence thereof; those of ordinary skill in the art work as can make various corresponding changes and modification according to the present invention, but these corresponding changes and distortion all should belong to the protection domain of the appended claim of the present invention.
Claims (5)
1. a gold is examined and silver-colored shell bimetal nano crystal, it is characterized in that, so that { the gold nuclear and the silver-colored shell bimetal nano crystal of 100} face have the crystalline form rule, comprise two cube triangle, regular cubes and have five heavy twin cross sections being the { club shaped structure of 100} type crystal face in the side simultaneously.
2. described gold nuclear of a claim 1 and silver-colored shell bimetal nano crystalline preparation method as solvent and reductive agent, and add certain density Silver Nitrate (AgNO with the higher polyhydroxy-alcohol of boiling point in solution
3), may further comprise the steps:
1) preparation gold nuclear stoste:
Compound concentration is the hydrochloro-auric acid (HAuCl of 0.05M-1M
44H
2O) and concentration be the polyhydroxy-alcohol solution of 1M-10M polyvinylpyrrolidone (PVP);
2) the silver-colored shell stoste of preparation:
Compound concentration is the PVP of 1M-10M and the Silver Nitrate (AgNO that concentration is 0.1mM-1M
3) polyhydroxy-alcohol solution;
3) preparation reactant mixing solutions:
3-1) the 0.05M-1M HAuCl for preparing according to step 1)
44H
2The polyhydroxy-alcohol solution of the 1M-10M polyvinylpyrrolidone of O and step 1) preparation, by hydrochloro-auric acid: the polyvinylpyrrolidone mol ratio is 1: 1-10, the mutual thorough mixing in hydrochloro-auric acid/Silver Nitrate mol ratio=500/1 obtain reactant mixing solutions 1;
3-2) get 0.1M-1M Silver Nitrate and 1M-10M polyvinylpyrrolidonesolution solution, by [AgNO
3]: the polyvinylpyrrolidone mol ratio is 1: the mutual thorough mixing of 1-10 obtains reactant mixing solutions 2; Wherein, described AgNO
3With respect to the mol ratio of hydrochloro-auric acid in the 1-20 scope;
4) nanocrystal of the silver-colored shell structure of synthetic gold nuclear:
4-1) with step 3-1) gained preparation gold nuclear stoste (reactant mixing solutions 1) is heated to boiling state in oil bath, kept 1-2 hour, again mixed solution naturally cooled to room temperature; It is centrifugal to take out the back, after supernatant liquor is separated, obtains Jin Jing and plants precipitation;
4-2) get above-mentioned steps 4-1) gained Jin Jing plants precipitation, joins step 2) in the preparation silver shell stoste (reactant mixing solutions 2) prepared, oil bath is heated to the solution boiling, keeps obtaining product solution more than 2 hours; Centrifugal then 10-30 minute, remove supernatant liquor, collecting precipitation thing and with deionized water (10-50mL) repetitive scrubbing precipitation obtains having based on { the gold nuclear and the silver-colored shell bimetal nano crystal of 100} face after centrifugal.
3. by described gold nuclear of claim 1 and silver-colored shell bimetal nano crystalline preparation method, it is characterized in that described polyhydroxy-alcohol comprises: ethylene glycol, 1,4-butyleneglycol, 1,5-pentanediol or tetraethylene-glycol.
4. by described gold nuclear of claim 1 and silver-colored shell bimetal nano crystalline preparation method, it is characterized in that described step 4-1) in centrifugal rotational speed be 3000rpm-6000rpm, centrifugal 10-30 minute.
5. by described gold nuclear of claim 1 and silver-colored shell bimetal nano crystalline preparation method, it is characterized in that described step 4-2) in centrifugal rotational speed be 10000rpm-15000rpm, kept 10-30 minute.
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