CN105014094B - Core-shell-structure silver-gold nanosheet based on epitaxial growth and preparation method and application thereof - Google Patents
Core-shell-structure silver-gold nanosheet based on epitaxial growth and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a core-shell-structure silver-gold nanosheet based on epitaxial growth and a preparation method and application thereof. The method includes the steps that firstly, a silver nanosheet solution is prepared, then, chloroauric acid and ligand react in the alkaline environment, and a gold precursor solution is obtained; and a reducing agent, surfactant, a pH modifier, ligand or acetonitrile and the silver nanosheet solution are added to the gold precursor solution, and the core-shell-structure silver-gold nanosheet is obtained after the reaction. The ligand and chloroauric acid radial can generate coordination, a gold precursor is formed, the redox potential of gold is reduced, and the replacement reaction is prevented from being generated; the gold precursor is reduced into gold atoms through the reducing agent, the gold atoms are deposited on the surface layer of a silver nanosheet in an epitaxial growth mode, and the core-shell-structure silver-gold nanosheet is formed. The preparation process is simple and feasible; the shape and the size of the core-shell-structure silver-gold nanosheet are controllable; the excellent stability and the good optical property are achieved; wide application prospects are achieved in the fields of molecular detection and the like.
Description
Technical field
The invention belongs to technical field of nano material, more particularly to a kind of Yin-gold based on epitaxially grown nucleocapsid structure
Nanometer sheet and its preparation method and application.
Background technology
Gold, silver have excellent optical property, and these properties come from its unique surface plasma body resonant vibration property, they
It is widely used in multiple fields, such as surface plasma strengthens Raman, surface plasma body resonant vibration enhancing fluorescence, photo-thermal and controls
The fields such as treatment, bio-imaging, catalysis.The position at the surface plasmon absorption peak of anisotropic gold, silver nanometer sheet can
To be adjusted near infrared region, this is most important in the application of biological field for gold, silver, because in this spectral region
The absorption of biological tissue, blood and water to light is minimum.
Scientist prepares Nano silver piece in calendar year 2001, after this preparation and optical property of the scientist to Nano silver piece
Numerous studies are carried out.The preparation method of Nano silver piece has the advantages that variation, high yield, simple, and Nano silver piece has
There is excellent optical property, these advantages make Nano silver piece show potential application prospect in some fields, but by
The extensive application of Nano silver piece is limited in the unstability and bio-toxicity of Nano silver piece.
In theory in the spectral region of ＞ 600nm, the optical property of gold-nano-piece connects with the optical property of Nano silver piece
Closely, better than the optical property of gold nano grain, gold utensil has easy functionalization, good stability and a biocompatibility, but Jenner
Rice piece is not widely studied and applied, and this there are problems that more mainly due to the preparation of gold-nano-piece, although iodine
Ion can improve the yield of gold-nano-piece, but gold-nano-piece yet suffers from the deficiencies such as low yield, monodispersity difference.It is simple high
The method for preparing gold-nano-piece produced becomes study hotspot.
In theory, epitaxial growth method can be combined with each other the advantage of the brilliant advantage of silver nanoparticle and gold.The lattice of Jin Yuyin
Constants very little, gold atom can pass through epitaxial deposition in the brilliant surface of silver nanoparticle, form the Yin-gold of nucleocapsid structure
It is nanocrystalline.It is this nanocrystalline with various properties and advantage, such as golden stability, easy functionalization, good biocompatibility
And optical property, the multiformity and excellent optical property of silver etc..Due to gold chloride oxidation-reduction potential than silver oxidation also
Former current potential is high, and the spontaneous generation displacement reaction of meeting, forms the nanocages or nanometer of electrum between gold chloride and silver nanoparticle crystalline substance
The structures such as framework, and the stability of these structures has problems.Scientist attempts can by adjusting thermodynamics of reactions and kinetics
To suppress displacement reaction, gold atom is set to be deposited on the brilliant surface of silver nanoparticle by epitaxially grown method, so as to obtain core-shell structure copolymer knot
Silver-the gold nanocrystals of structure.Kinetics adjust the main pH value for including regulation reaction system and add speed of golden presoma etc.；Heating power
Learn to adjust and then mainly reduce the oxidation-reduction potential of gold by selecting suitable part.But these methods are still present not
Foot, such as long preparation period, process are complicated, there are problems that displacement.
The content of the invention
It is an object of the invention to provide a kind of silver-gold-nano-piece and its preparation based on epitaxially grown nucleocapsid structure
Methods and applications, the method can make gold atom in the epitaxial growth of Nano silver piece surface, obtained nucleocapsid structure silver-gold nano
Piece has excellent stability and optical property, has a good application prospect in organic molecule context of detection.
To reach above-mentioned purpose, the technical solution used in the present invention is：
A kind of preparation method of the silver-gold-nano-piece based on epitaxially grown nucleocapsid structure, comprises the following steps：
1) Nano silver piece solution is prepared
Silver nitrate is added to the water, silver nitrate solution is configured to, trisodium citrate, hydrogen peroxide are then sequentially added thereto
And sodium borohydride aqueous solution, 0.2～6h is stirred, obtain Nano silver piece solution；Wherein silver nitrate, trisodium citrate, hydrogen peroxide, boron
The mol ratio of sodium hydride is 1:(5～100):(50～1000):(1～50)；
2) precursor solution of gold is prepared
Gold chloride, part and pH adjusting agent are added to the water, the mixed liquor that pH value is 8～12 is obtained, by mixed liquor 4～
0.5～72h is stood at 80 DEG C, the precursor solution of gold is obtained；Wherein gold chloride and the mol ratio of part are 1:(3～15)；
3) nucleocapsid structure silver-gold-nano-piece is prepared
Water is added in the precursor solution of gold, the precursor water solution of gold is configured to, surface work is then added thereto to
Property agent and reducing agent, and add acetonitrile or part, make gold element in the precursor water solution of gold, reducing agent, surfactant,
The mol ratio of acetonitrile is 1:(1～100):(1～1000):(100～20000), or make the gold in the precursor water solution of gold
Element, reducing agent, surfactant, the mol ratio of part are 1:(1～100):(1～1000):(1～100), is subsequently adding pH
PH value is adjusted to 8～12 by regulator, adds Nano silver piece solution, obtains mixture, gold element and silver element in mixture
Mol ratio is 1:(1～6), by mixture at 4～80 DEG C 0.5～72h of standing and reacting, reaction terminate after by product centrifugation, wash
Wash, that is, obtain the silver-gold-nano-piece of nucleocapsid structure.
The step 1) in silver nitrate solution concentration be 1 × 10-5～1 × 10-3mol/L；
The step 2) in mixed liquor the concentration of gold chloride be 1 × 10-5～2 × 10-1mol/L；
The step 3) in gold precursor water solution concentration be 1 × 10-6～1 × 10-2mol/L。
In step 2) carry out before first to step 1) obtained in the size of Nano silver piece in Nano silver piece solution be adjusted,
Specifically regulating step is：Take volume for V1 the step of 1) obtained in Nano silver piece solution, be dispersed in water after being centrifuged, obtain
Volume for V2 Nano silver piece dispersion liquid, V1:V2=1:(0.5～10), in Nano silver piece dispersion liquid trisodium citrate is added
And ascorbic acid, solution A is obtained, the molar concentration of ascorbic acid is 1 × 10 in solution A-5～1 × 10-1Mol/L, citric acid three
The molar concentration of sodium is 1 × 10-5～1 × 10-2mol/L；The mixed aqueous solution of sodium citrate and silver nitrate is prepared, B is designated as molten
Liquid, the concentration of silver nitrate is 1 × 10 in B solution-5～1 × 10-2Mol/L, the molar concentration of trisodium citrate is 1 × 10-5～1
×10-2mol/L；B solution is added dropwise in solution A, is reacted at room temperature, can when the ultraviolet of reaction system is measured
When seeing that near ir absorption peaks are less than or equal to 3000nm more than 600nm, stop Deca B solution, obtain various sizes of Nano silver piece
Solution.
The average-size of the Nano silver piece in Nano silver piece solution after regulation is 30nm～5 μm.
Described part is sulphite, bisulfites or thiosulfate.
Described pH adjusting agent is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, phosphorus
Sour disodium hydrogen, dipotassium hydrogen phosphate or ammonia.
Described surfactant is polyvinylpyrrolidone, polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer
Thing, dodecyl sodium sulfate or cetyl trimethylammonium bromide.
Described reducing agent is ascorbic acid, oxammonium hydrochloride., formaldehyde, hydrazine hydrate or boron hydride.
Nucleocapsid structure obtained in the described preparation method based on the silver-gold-nano-piece of epitaxially grown nucleocapsid structure
Silver-gold-nano-piece, the silver-gold-nano-piece is made up of kernel portion and casing part, wherein kernel portion be Nano silver piece, shell
Part is the gold nano layer gone out by epitaxial growth on Nano silver piece.
Application of the silver-gold-nano-piece of described nucleocapsid structure in the Raman substrate for detecting organic molecule is prepared.
Compared with prior art, the beneficial effects of the present invention is：
The preparation method of the silver-gold-nano-piece based on epitaxially grown nucleocapsid structure that the present invention is provided, first with silver nitrate
Nano silver piece solution is obtained for raw material, it is then that gold chloride and part is soluble in water, add pH adjusting agent adjust pH value be 8～
12, reaction obtains the precursor solution of gold；Again by reducing agent, surfactant, pH adjusting agent, part or acetonitrile, Nano silver piece
Solution is added in the precursor solution of gold, and reaction obtains nucleocapsid structure Fa Yin-gold-nano-piece.Part can be with chlorine in the present invention
There is the presoma that coordination forms gold, the oxidation-reduction potential ratio of the golden presoma obtained by coordination in auric acid root
The oxidation-reduction potential of silver is low, can reduce the oxidation-reduction potential of gold, so as to the presoma for preventing gold occurs with Nano silver piece
Displacement reaction, while part will not produce serious etching to silver strip.The present invention, will using reducing agent using Nano silver piece as seed
The presoma of gold is reduced to gold atom, and gold atom is coated on the top layer of Nano silver piece by epitaxially grown mode, in silver nanoparticle
The epitaxial growth of piece surface, forms the silver-gold-nano-piece of nucleocapsid structure.The preparation process of the present invention is simple, preparation method letter
Just, cycle is short, yield is high, reproducible, is adapted to large-scale production.The pattern of the silver-gold-nano-piece of obtained nucleocapsid structure and
Size is controllable, and the silver-gold-nano-piece of the nucleocapsid structure of preparation has the advantages that excellent stability and good optical property,
The fields such as organic molecule detection have broad application prospects.
Further, the present invention, can be to the Nano silver piece in Nano silver piece solution after prepared Nano silver piece solution
Size is adjusted such that it is able to provide various sizes of Nano silver piece as seed；And by using various sizes of silver
Nanometer sheet can prepare the silver-gold-nano-piece of various sizes of nucleocapsid structure as seed；And by controlling reaction condition
Deposition of the gold atom on Nano silver piece can be adjusted；And the different growth conditionss of control can be passed through, make obtained core-
Silver-the gold-nano-piece of shell structure presents various structures.
Further, the silver-gold-nano-piece of the obtained nucleocapsid structure of the present invention shows good stability and optical
Matter, by the silver-gold-nano-piece of the nucleocapsid structure measuring stability in the corrosive atmospheres such as hydrogen peroxide, ferric chloride is placed in, test
As a result show that the stability of the silver-gold-nano-piece of the nucleocapsid structure is consistent with the stability of gold；And the silver of the nucleocapsid structure-
Gold-nano-piece has excellent surface plasma body resonant vibration performance, the silver-gold-nano-piece of nucleocapsid structure is used as into Raman matrix and is used
In the detection of organic molecule (such as crystal violet), as a result show：Crystal violet carries out Raman inspection in solid phase with the laser that wavelength is 532nm
Survey, the concentration limit of detection is up to 10-8mol/L；Crystal violet molecule carries out Raman detection in water with the laser that wavelength is 633nm,
Detectable concentration limit in water can reach 10-7Mol/L, therefore the silver-gold-nano-piece of nucleocapsid structure is expected to obtained in the present invention
To extensively application, especially in biological field.
Description of the drawings
Fig. 1 is the transmission electron micrograph of the silver-gold-nano-piece of nucleocapsid structure obtained in the embodiment of the present invention 1.
Fig. 2 is the transmission electron micrograph and height of the silver-gold-nano-piece of nucleocapsid structure obtained in the embodiment of the present invention 2
Angle annular dark field-scanning projection electron transmission micrographs piece, wherein (a) is transmission electron micrograph, (b) it is high angle
Annular dark field-scanning projection electron transmission micrographs piece.
Fig. 3 is the transmission electron micrograph of the silver-gold-nano-piece of nucleocapsid structure obtained in the embodiment of the present invention 3.
Fig. 4 is the transmission electron microscope photo of the silver-gold-nano-piece of nucleocapsid structure obtained in the embodiment of the present invention 4.
Fig. 5 is the transmission electron microscope photo of the silver-gold-nano-piece of nucleocapsid structure obtained in the embodiment of the present invention 5.
Fig. 6 is the transmission electron microscope photo of the silver-gold-nano-piece of nucleocapsid structure obtained in the embodiment of the present invention 6.
Fig. 7 is the silver-gold-nano-piece of nucleocapsid structure obtained in the embodiment of the present invention 1 in strong oxidizing property and corrosive environment
Transmission electron microscope photo after middle stability test, wherein (a) is the transmitted electron in hydrogen peroxide after stability test showing
Micro mirror photo, is (b) the transmission electron microscope photo after stability test in ferric chloride.
Fig. 8 strengthens test for the Raman of the silver-gold-nano-piece of nucleocapsid structure obtained in the embodiment of the present invention 1, wherein (a) is
Silver-the gold-nano-piece of nucleocapsid structure strengthens test to the Raman of crystal violet (CV) in atmosphere, is (b) Yin-gold of nucleocapsid structure
Nanometer sheet strengthens test in water to the Raman of CV.
Specific embodiment
Several preferably embodiments of the present invention are given below, are that the present invention is further illustrated, rather than limit this
The scope of invention.
Embodiment 1:
(1) silver nitrate is added to the water so as to which molar concentration is 1 × 10-4Mol/L, adds afterwards trisodium citrate, dioxygen
Water, is then quickly added into sodium borohydride aqueous solution, and silver nitrate, trisodium citrate, hydrogen peroxide, the mol ratio of sodium borohydride are 1:
45:240:6,0.5h is stirred, obtain Nano silver piece solution.The UV, visible light near ir absorption peaks of the Nano silver piece solution are
600nm, the average-size of the Nano silver piece in the Nano silver piece solution is 30nm.
(2) precursor solution of gold is prepared.Gold chloride, part (sodium sulfite), pH adjusting agent (sodium hydroxide) are added
In water, the concentration for making gold chloride is 1.25 × 10-3Mol/L, gold chloride is 1 with the mol ratio of part:3, the pH value of solution is 10,
12h is stood at 25 DEG C, the precursor solution of gold is obtained.
(3) nucleocapsid structure silver-gold-nano-piece is prepared.The precursor concentration of configuration gold is 5 × 10-4The aqueous solution of mol/L,
Surfactant (polyvinylpyrrolidone), reducing agent (ascorbic acid), part (sodium sulfite) are added, gold element, reduction is made
Agent, surfactant, the mol ratio of sodium sulfite are 1:20:100:1, the pH value for adding sodium hydrate regulator solution is 8, takes step
Suddenly add in above-mentioned solution after the Nano silver piece solution centrifugal that prepared by (1), make GOLD FROM PLATING SOLUTION be 1 with the mol ratio of silver:1,30
12h is stood at DEG C, centrifuge washing obtains the silver-gold-nano-piece of nucleocapsid structure.
Fig. 1 is the transmission electron micrograph of the silver-gold-nano-piece of nucleocapsid structure obtained in the embodiment of the present invention 1.Fig. 1
A the light-colored part of nanometer sheet is silver in (), (b), dark parts are gold, and Nano silver piece is coated by golden shell layer.
Embodiment 2:
(1) silver nitrate is added to the water so as to which molar concentration is 1 × 10-4Mol/L, adds afterwards trisodium citrate, dioxygen
Water, is then quickly added into sodium borohydride aqueous solution, and silver nitrate, trisodium citrate, hydrogen peroxide, the mol ratio of sodium borohydride are 1:
80:350:18,2h is stirred, obtain Nano silver piece solution.
(2) precursor solution of gold is prepared.Gold chloride, part (sodium sulfite), pH adjusting agent (sodium hydroxide) are added
In water, the concentration for making gold chloride is 5 × 10-4Mol/L, gold chloride is 1 with the mol ratio of part:3, the pH value of solution is 12,
8h is stood at 30 DEG C, the precursor solution of gold is obtained.
(3) nucleocapsid structure silver-gold-nano-piece is prepared.The precursor concentration of configuration gold is 5 × 10-4The aqueous solution of mol/L,
Surfactant (polyvinylpyrrolidone), reducing agent (ascorbic acid), acetonitrile are added, makes golden presoma, reducing agent, surface live
Property agent, acetonitrile mol ratio be 1:20:100:4000, the pH value for adding sodium hydrate regulator solution is 10, takes step (1) preparation
Nano silver piece solution centrifugal after add in above-mentioned solution, make GOLD FROM PLATING SOLUTION with silver mol ratio be 1:1,16h is stood at 25 DEG C,
Centrifuge washing, obtains the silver-gold-nano-piece of nucleocapsid structure.
Fig. 2 is the transmission electron micrograph and height of the silver-gold-nano-piece of nucleocapsid structure obtained in the embodiment of the present invention 2
Angle annular dark field-scanning projection electron transmission micrographs piece, wherein (a) is transmission electron micrograph, nanometer in picture
The light areas of piece are silver, and dark parts are gold, are (b) high angle annular dark field-scanning projection electron transmission micrographs piece, figure
Nanometer sheet edge bright areas are gold in piece, and middle dull areas are silver；Nano silver piece is coated by golden shell layer, overall hexagonal
Etc. structure.
Embodiment 3:
(1) silver nitrate is added to the water so as to which molar concentration is 1 × 10-4Mol/L, adds afterwards trisodium citrate, dioxygen
Water, is then quickly added into sodium borohydride aqueous solution, and silver nitrate, trisodium citrate, hydrogen peroxide, the mol ratio of sodium borohydride are 1:
60:300:10,1h is stirred, obtain Nano silver piece solution.
(2) precursor solution of gold is prepared.Gold chloride, part (sodium sulfite), pH adjusting agent (potassium hydroxide) are added
In water, the concentration for making gold chloride is 5 × 10-3Mol/L, gold chloride is 1 with the mol ratio of part:5, the pH value of solution is 10,
8h is stood at 25 DEG C, the precursor solution of gold is obtained.
(3) nucleocapsid structure silver-gold-nano-piece is prepared.The precursor concentration of configuration gold is 1 × 10-3The aqueous solution of mol/L,
Surfactant (polyvinylpyrrolidone), reducing agent (ascorbic acid), part are added, makes golden presoma, reducing agent, surface live
Property agent, part mol ratio be 1:10:40:1, add the pH value that potassium hydroxide adjusts solution to be 10, take the silver of step (1) preparation
During above-mentioned solution is added after nanometer sheet solution centrifugal, GOLD FROM PLATING SOLUTION is set to be 1 with the mol ratio of silver:1,12h, centrifugation are stood at 30 DEG C
Washing, obtains the silver-gold-nano-piece of nucleocapsid structure.
Fig. 3 for nucleocapsid structure obtained in the embodiment of the present invention 3 silver-gold-nano-piece transmission electron micrograph, Fig. 3
The light-colored part of middle nanometer sheet is silver, and dark parts are gold, and Nano silver piece is coated by golden shell layer.
Embodiment 4:
(1) silver nitrate is added to the water so as to which molar concentration is 1 × 10-4Mol/L, adds afterwards trisodium citrate, dioxygen
Water, is then quickly added into sodium borohydride aqueous solution, and silver nitrate, trisodium citrate, hydrogen peroxide, the mol ratio of sodium borohydride are 1:
45:250:6,0.5h is stirred, obtain Nano silver piece solution.
(2) take after the Nano silver piece solution that the step of volume is V1 prepared by (1) is centrifuged and be dispersed in water, obtain volume
For the Nano silver piece dispersion liquid of V2, V1:V2=1:1, trisodium citrate and ascorbic acid are added in Nano silver piece dispersion liquid, make
The molar concentration of ascorbic acid is 1.5 × 10-3Mol/L, the molar concentration of trisodium citrate is 5 × 10-4Mol/L, this mixing is molten
Liquid is designated as solution A；The mixed aqueous solution of sodium citrate and silver nitrate is prepared, the molar concentration for making silver nitrate is 7.5 × 10-4mol/
L, the molar concentration of trisodium citrate is 5 × 10-4Mol/L, this mixed solution is designated as B solution；B solution is added dropwise to into A molten
In liquid, reacted at room temperature, when the UV, visible light near ir absorption peaks for measuring reaction system are located at 880nm, stopped
Deca B solution (stopped reaction), the average-size of Nano silver piece is 175nm in the Nano silver piece solution for obtaining.
(3) precursor solution of gold is prepared.Gold chloride, part (sodium sulfite), pH adjusting agent (potassium carbonate) are added into water
In, the concentration for making gold chloride is 5 × 10-3Mol/L, gold chloride is 1 with the mol ratio of part:3, the pH value of solution is 8, at 60 DEG C
Lower standing 4h, obtains the precursor solution of gold.
(4) nucleocapsid structure silver-gold-nano-piece is prepared.The precursor concentration of configuration gold is 5 × 10-4The aqueous solution of mol/L,
Surfactant (polyvinylpyrrolidone), reducing agent (ascorbic acid), part (sodium sulfite) are added, golden presoma is made, is gone back
Former agent, surfactant, the mol ratio of part are 1:16:100:4, add the pH value that potassium carbonate adjusts solution to be 10, take step
(1) add in above-mentioned solution after the Nano silver piece solution centrifugal for preparing, make GOLD FROM PLATING SOLUTION be 1 with the mol ratio of silver:2, at 40 DEG C
6h is stood, centrifuge washing obtains the silver-gold-nano-piece of nucleocapsid structure.
Fig. 4 is the transmission electron microscope photo of the silver-gold-nano-piece of nucleocapsid structure obtained in the embodiment of the present invention 4, schemes
The light-colored part of middle nanometer sheet is silver, and dark parts are gold, and Nano silver piece is coated by golden shell layer, and the edge of outer layer gold is in sawtooth
Shape.
Embodiment 5:
(1) silver nitrate is added to the water so as to which molar concentration is 1 × 10-4Mol/L, adds afterwards trisodium citrate, dioxygen
Water, is then quickly added into sodium borohydride aqueous solution, and silver nitrate, trisodium citrate, hydrogen peroxide, the mol ratio of sodium borohydride are 1:
45:250:6,0.5h is stirred, obtain Nano silver piece solution.
(2) take after the Nano silver piece solution that the step of volume is V1 prepared by (1) is centrifuged and be dispersed in water, obtain volume
For the Nano silver piece dispersion liquid of V2, V1:V2=1:0.5, trisodium citrate and ascorbic acid are added in Nano silver piece dispersion liquid,
The molar concentration for making ascorbic acid is 4 × 10-4Mol/L, the molar concentration of trisodium citrate is 1 × 10-3Mol/L, this mixing is molten
Liquid is designated as solution A；The mixed aqueous solution of sodium citrate and silver nitrate is prepared, the molar concentration for making silver nitrate is 4 × 10-4Mol/L,
The molar concentration of trisodium citrate is 2 × 10-4Mol/L, this mixed solution is designated as B solution；B solution is added dropwise to into solution A
In, reacted at room temperature, when the UV, visible light near ir absorption peaks for measuring reaction system are located at 780nm, stop drop
Plus B solution (stopped reaction), the average-size of Nano silver piece is 132nm in the Nano silver piece solution for obtaining.
(3) precursor solution of gold is prepared.Gold chloride, part (sodium sulfite), pH adjusting agent (sodium bicarbonate) are added
In water, the concentration for making gold chloride is 1 × 10-3Mol/L, gold chloride is 1 with the mol ratio of part:5, the pH value of solution is 10,
8h is stood at 40 DEG C, the precursor solution of gold is obtained.
(4) nucleocapsid structure silver-gold-nano-piece is prepared.The precursor concentration of configuration gold is 5 × 10-4The aqueous solution of mol/L,
Surfactant (polyvinylpyrrolidone), reducing agent (ascorbic acid), part (sodium sulfite) are added, golden presoma is made, is gone back
Former agent, surfactant, the mol ratio of part are 1:12:40:6, the pH value for adding manganese hydrogen sodium regulating solution is 10, takes step
(1) add in above-mentioned solution after the Nano silver piece solution centrifugal for preparing, make GOLD FROM PLATING SOLUTION be 1 with the mol ratio of silver:4, at 40 DEG C
6h is stood, centrifuge washing obtains the silver-gold-nano-piece of nucleocapsid structure.
Fig. 5 is the transmission electron microscope photo of the silver-gold-nano-piece of nucleocapsid structure obtained in the embodiment of the present invention 5, schemes
The light-colored part of middle nanometer sheet is silver, and dark parts are gold, and Nano silver piece is coated by golden shell layer.
Embodiment 6:
(1) silver nitrate is added to the water so as to which molar concentration is 1 × 10-4Mol/L, adds afterwards trisodium citrate, dioxygen
Water, is then quickly added into sodium borohydride aqueous solution, and silver nitrate, trisodium citrate, hydrogen peroxide, the mol ratio of sodium borohydride are 1:
80:350:18,2h is stirred, obtain Nano silver piece solution.
(2) take after the Nano silver piece solution that the step of volume is V1 prepared by (1) is centrifuged and be dispersed in water, obtain volume
For the Nano silver piece dispersion liquid of V2, V1:V2=1:0.5, trisodium citrate and ascorbic acid are added in Nano silver piece dispersion liquid,
The molar concentration for making ascorbic acid is 2 × 10-3Mol/L, the molar concentration of trisodium citrate is 2 × 10-3Mol/L, this mixing is molten
Liquid is designated as solution A；The mixed aqueous solution of sodium citrate and silver nitrate is prepared, the molar concentration for making silver nitrate is 1 × 10-4Mol/L,
The molar concentration of trisodium citrate is 1 × 10-4Mol/L, this mixed solution is designated as B solution；B solution is added dropwise to into solution A
In, reacted at room temperature, when the UV, visible light near ir absorption peaks for measuring reaction system are located at 780nm, stop drop
Plus B solution (stopped reaction), the average-size of Nano silver piece is 218nm in the Nano silver piece solution for obtaining.
(3) precursor solution of gold is prepared.Gold chloride, part (sodium sulfite), pH adjusting agent (sodium hydroxide) are added
In water, the concentration for making gold chloride is 5 × 10-4Mol/L, gold chloride is 1 with the mol ratio of part:3, the pH value of solution is 12,
1h is stood at 80 DEG C of temperature, the precursor solution of gold is obtained.
(4) nucleocapsid structure silver-gold-nano-piece is prepared.The precursor concentration of configuration gold is 5 × 10-4The aqueous solution of mol/L,
Surfactant (polyvinylpyrrolidone), reducing agent (ascorbic acid), part (sodium sulfite) are added, golden presoma is made, is gone back
Former agent, surfactant, the mol ratio of part are 1:20:100:2, the pH value for adding sodium hydrate regulator solution is 12, takes step
Suddenly add in above-mentioned solution after the Nano silver piece solution centrifugal that prepared by (1), make GOLD FROM PLATING SOLUTION be 1 with the mol ratio of silver:6,25
DEG C 12h is stood, centrifuge washing obtains the silver-gold-nano-piece of nucleocapsid structure.
Fig. 6 is the transmission electron microscope photo of the silver-gold-nano-piece of nucleocapsid structure obtained in the embodiment of the present invention 6, schemes
The light-colored part of middle nanometer sheet is silver, and dark parts are gold, and Nano silver piece is coated by golden shell layer.
Embodiment 7:
(1) silver nitrate is added to the water so as to which molar concentration is 5 × 10-4Mol/L, adds afterwards trisodium citrate, dioxygen
Water, is then quickly added into sodium borohydride aqueous solution, and silver nitrate, trisodium citrate, hydrogen peroxide, the mol ratio of sodium borohydride are 1:
25:500:30,3h is stirred, obtain Nano silver piece solution.
(2) precursor solution of gold is prepared.By gold chloride, part (sodium sulfite), pH adjusting agent (dipotassium hydrogen phosphate)
It is added to the water, the concentration for making gold chloride is 1 × 10-4Mol/L, gold chloride is 1 with the mol ratio of part:8, the pH value of solution is
8.5,50h is stood at 15 DEG C, obtain the precursor solution of gold.
(3) nucleocapsid structure silver-gold-nano-piece is prepared.The precursor concentration of configuration gold is 1 × 10-5The aqueous solution of mol/L,
Surfactant (cetyl trimethylammonium bromide), reducing agent (hydrazine hydrate), acetonitrile are added, golden presoma, reducing agent, table is made
Face activating agent, the mol ratio of acetonitrile are 1:1:1:100, add the pH value that dipotassium hydrogen phosphate adjusts solution to be 8.5, take step (1)
Add in above-mentioned solution after the Nano silver piece solution centrifugal of preparation, make GOLD FROM PLATING SOLUTION be 1 with the mol ratio of silver:3.5, it is quiet at 10 DEG C
50h is put, centrifuge washing obtains the silver-gold-nano-piece of nucleocapsid structure.
Embodiment 8:
(1) silver nitrate is added to the water so as to which molar concentration is 5 × 10-3Mol/L, adds afterwards trisodium citrate, dioxygen
Water, is then quickly added into sodium borohydride aqueous solution, and silver nitrate, trisodium citrate, hydrogen peroxide, the mol ratio of sodium borohydride are 1:
90:800:40,4h is stirred, obtain Nano silver piece solution.
(2) precursor solution of gold is prepared.Gold chloride, part (potassium sulfite), pH adjusting agent (sodium carbonate) are added into water
In, the concentration for making gold chloride is 1 × 10-2Mol/L, gold chloride is 1 with the mol ratio of part:12, the pH value of solution is 10.5,
30h is stood at 50 DEG C, the precursor solution of gold is obtained.
(3) nucleocapsid structure silver-gold-nano-piece is prepared.The precursor concentration of configuration gold is 5 × 10-3The aqueous solution of mol/L,
Surfactant (dodecyl sodium sulfate), reducing agent (sodium borohydride), acetonitrile are added, makes golden presoma, reducing agent, surface live
Property agent, acetonitrile mol ratio be 1:100:1000:20000, the pH value for adding sodium carbonate regulating solution is 10.5, takes step (1)
Add in above-mentioned solution after the Nano silver piece solution centrifugal of preparation, make GOLD FROM PLATING SOLUTION be 1 with the mol ratio of silver:2.5, it is quiet at 60 DEG C
20h is put, centrifuge washing obtains the silver-gold-nano-piece of nucleocapsid structure.
Embodiment 9:
(1) silver nitrate is added to the water so as to which molar concentration is 1 × 10-5Mol/L, adds afterwards trisodium citrate, dioxygen
Water, is then quickly added into sodium borohydride aqueous solution, and silver nitrate, trisodium citrate, hydrogen peroxide, the mol ratio of sodium borohydride are 1:5:
50:1,0.2h is stirred, obtain Nano silver piece solution.
(2) take after the Nano silver piece solution that the step of volume is V1 prepared by (1) is centrifuged and be dispersed in water, obtain volume
For the Nano silver piece dispersion liquid of V2, V1:V2=1:5, trisodium citrate and ascorbic acid are added in Nano silver piece dispersion liquid, make
The molar concentration of ascorbic acid is 1 × 10-5Mol/L, the molar concentration of trisodium citrate is 1 × 10-5Mol/L, this mixed solution
It is designated as solution A；The mixed aqueous solution of sodium citrate and silver nitrate is prepared, the molar concentration for making silver nitrate is 1 × 10-5Mol/L, lemon
The molar concentration of lemon acid trisodium is 1 × 10-5Mol/L, this mixed solution is designated as B solution；B solution is added dropwise in solution A,
Reacted at room temperature, when the UV, visible light near ir absorption peaks for measuring reaction system are located at 1810nm, stopped Deca B
Solution (stopped reaction), the average-size of Nano silver piece is 2.1 μm in the Nano silver piece solution for obtaining.
(3) precursor solution of gold is prepared.Gold chloride, part (sodium thiosulfate), pH adjusting agent (ammonia) are added into water
In, the concentration for making gold chloride is 1 × 10-5Mol/L, gold chloride is 1 with the mol ratio of part:15, the pH value of solution is 9, in temperature
72h is stood at 4 DEG C of degree, the precursor solution of gold is obtained.
(4) nucleocapsid structure silver-gold-nano-piece is prepared.The precursor concentration of configuration gold is 1 × 10-6The aqueous solution of mol/L,
Add surfactant (polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer), reducing agent (oxammonium hydrochloride .), part
(sodium thiosulfate), makes golden presoma, reducing agent, surfactant, the mol ratio of part be 1:1:1:10, add ammonia to adjust
The pH value of solution is 9, is added in above-mentioned solution after the Nano silver piece solution centrifugal for taking step (1) preparation, makes GOLD FROM PLATING SOLUTION with silver
Mol ratio be 1:3,72h is stood at 4 DEG C, centrifuge washing obtains the silver-gold-nano-piece of nucleocapsid structure.
Embodiment 10:
(1) silver nitrate is added to the water so as to which molar concentration is 1 × 10-3Mol/L, adds afterwards trisodium citrate, dioxygen
Water, is then quickly added into sodium borohydride aqueous solution, and silver nitrate, trisodium citrate, hydrogen peroxide, the mol ratio of sodium borohydride are 1:
100:1000:50,6h is stirred, obtain Nano silver piece solution.
(2) take after the Nano silver piece solution that the step of volume is V1 prepared by (1) is centrifuged and be dispersed in water, obtain volume
For the Nano silver piece dispersion liquid of V2, V1:V2=1:10, trisodium citrate and ascorbic acid are added in Nano silver piece dispersion liquid,
The molar concentration for making ascorbic acid is 1 × 10-1Mol/L, the molar concentration of trisodium citrate is 1 × 10-2Mol/L, this mixing is molten
Liquid is designated as solution A；The mixed aqueous solution of sodium citrate and silver nitrate is prepared, the molar concentration for making silver nitrate is 1 × 10-2Mol/L,
The molar concentration of trisodium citrate is 1 × 10-2Mol/L, this mixed solution is designated as B solution；B solution is added dropwise to into solution A
In, reacted at room temperature, when the UV, visible light near ir absorption peaks for measuring reaction system are located at 3000nm, stop drop
Plus B solution (stopped reaction), the average-size of Nano silver piece is 5 μm in the Nano silver piece solution for obtaining.
(3) precursor solution of gold is prepared.Gold chloride, part (Potassium acid sulfite), pH adjusting agent (potassium bicarbonate) are added
In entering water, the concentration for making gold chloride is 2 × 10-1Mol/L, gold chloride is 1 with the mol ratio of part:10, the pH value of solution is 8,
0.5h is stood at 75 DEG C of temperature, the precursor solution of gold is obtained.
(4) nucleocapsid structure silver-gold-nano-piece is prepared.The precursor concentration of configuration gold is 1 × 10-2The aqueous solution of mol/L,
Surfactant (dodecyl sodium sulfate), reducing agent (formaldehyde), part (Potassium acid sulfite) are added, golden presoma, reduction is made
Agent, surfactant, the mol ratio of part are 1:100:1000:100, add the pH value that potassium bicarbonate adjusts solution to be 8, take step
Suddenly add in above-mentioned solution after the Nano silver piece solution centrifugal that prepared by (1), make GOLD FROM PLATING SOLUTION be 1 with the mol ratio of silver:5,80
DEG C 0.5h is stood, centrifuge washing obtains the silver-gold-nano-piece of nucleocapsid structure.
The stability of silver-gold-nano-piece to nucleocapsid structure obtained in the present invention and answering in detection organic molecule below
With being described in detail.
1st, stability test
Stability test is carried out to obtained nucleocapsid structure silver-gold-nano-piece, by nucleocapsid structure silver-gold-nano-piece difference
In being scattered in the strong oxidizing properties and corrosive atmosphere such as hydrogen peroxide, ferric chloride, nitric acid, its stability is tested.
Specially：Respectively silver-the gold-nano-piece of nucleocapsid structure obtained in embodiment 1 is scattered in into concentration for the double of 1mol/L
In oxygen water, 0.5mol/L ferric chlorides, 12h is stood at 20 DEG C, centrifuge washing shoots transmission electron microscope photo, as a result
As shown in Figure 7.Fig. 7 is steady in hydrogen peroxide and ferric chloride for the silver-gold-nano-piece of nucleocapsid structure obtained in the embodiment of the present invention 1
Transmission electron microscope photo after qualitative test, wherein (a) is the transmission electron microscope in hydrogen peroxide after stability test
Photo, is (b) the transmission electron microscope photo after stability test in ferric chloride.It can be seen that nucleocapsid structure from 7 figures
The pattern of silver-gold-nano-piece do not change, remain in that overall pattern.Illustrate obtained nucleocapsid structure of the invention
Silver-gold-nano-piece has excellent stability in hydrogen peroxide, ferric chloride etc. are with strong oxidizing property and corrosive environment.
2nd, for detecting organic molecule
Silver-the gold-nano-piece of obtained nucleocapsid structure of the invention can be used in detecting organic molecule.
It is to the concrete grammar that organic molecule (crystal violet) carries out Raman detection：By core-shell structure copolymer obtained in the embodiment of the present invention 1
The hanging drop of the silver-gold-nano-piece of structure is added on several silicon chips, after being dried at room temperature for, makes the silver-Jenner of nucleocapsid structure
Rice piece is transferred on silicon chip；Deca concentration is 10 on the silver-gold-nano-piece for be transferred into the nucleocapsid structure of silicon chip-6mol/L
To 10-8Crystal violet (CV) solution of mol/L, and a kind of crystal violet solution of concentration of Deca on each silicon chip, then spontaneously dry
And Raman sign is carried out with the Raman instrument for being equipped with wavelength 514nm, shown in Raman detection result such as Fig. 8 (a)：As a result enforcement is shown
The sensitivity of the silver of the nucleocapsid structure that example 1 is obtained-gold-nano-piece Raman detection can reach 10-8mol/L.Or implement the present invention
Silver-the gold-nano-piece of nucleocapsid structure obtained in example 1 is scattered in respectively concentration for 10-5Mol/L to 10-7In the CV solution of mol/L,
2h is stood, Raman sign is carried out with the Raman instrument for being equipped with wavelength 633nm, shown in Raman detection result such as Fig. 8 (b)：As a result show
The sensitivity for showing the silver-Raman detection of the gold-nano-piece in water of the nucleocapsid structure that embodiment 1 is obtained can reach 10-7mol/L。
Claims (9)
1. a kind of preparation method of the silver-gold-nano-piece based on epitaxially grown nucleocapsid structure, it is characterised in that including following
Step：
1) Nano silver piece solution is prepared
Silver nitrate is added to the water, silver nitrate solution is configured to, trisodium citrate, hydrogen peroxide and boron are then sequentially added thereto
Sodium hydride aqueous solution, stirs 0.2～6h, obtains Nano silver piece solution；Wherein silver nitrate, trisodium citrate, hydrogen peroxide, hydroboration
The mol ratio of sodium is 1:(5～100):(50～1000):(1～50)；
2) precursor solution of gold is prepared
Gold chloride, part and pH adjusting agent are added to the water, the mixed liquor that pH value is 8～12 are obtained, by mixed liquor at 4～80 DEG C
0.5～72h of lower standing, obtains the precursor solution of gold；Wherein gold chloride and the mol ratio of part are 1:(3～15)；Described
Part is sulphite, bisulfites or thiosulfate；
3) nucleocapsid structure silver-gold-nano-piece is prepared
Water is added in the precursor solution of gold, the precursor water solution of gold is configured to, surfactant is then added thereto to
And reducing agent, and acetonitrile or part are added, make gold element, reducing agent, surfactant, acetonitrile in the precursor water solution of gold
Mol ratio be 1:(1～100):(1～1000):(100～20000), or make gold precursor water solution in gold element,
Reducing agent, surfactant, the mol ratio of part are 1:(1～100):(1～1000):(1～100), is subsequently adding pH regulator
PH value is adjusted to 8～12 by agent, adds Nano silver piece solution, obtains mixture, in mixture gold element and silver element mole
Than for 1:(1～6), by mixture at 4～80 DEG C 0.5～72h of standing and reacting, reaction terminate after by product centrifugation, washing, i.e.,
Obtain the silver-gold-nano-piece of nucleocapsid structure.
2. the preparation method of the silver-gold-nano-piece based on epitaxially grown nucleocapsid structure according to claim 1, it is special
Levy and be：The step 1) in silver nitrate solution concentration be 1 × 10-5～1 × 10-3mol/L；
The step 2) in mixed liquor the concentration of gold chloride be 1 × 10-5～2 × 10-1mol/L；
The step 3) in gold precursor water solution concentration be 1 × 10-6～1 × 10-2mol/L。
3. the preparation method of the silver-gold-nano-piece based on epitaxially grown nucleocapsid structure according to claim 1, it is special
Levy and be：In step 2) carry out before first to step 1) obtained in the size of Nano silver piece in Nano silver piece solution be adjusted,
Specifically regulating step is：Take volume for V1 the step of 1) obtained in Nano silver piece solution, be dispersed in water after being centrifuged, obtain
Volume for V2 Nano silver piece dispersion liquid, V1:V2=1:(0.5～10), in Nano silver piece dispersion liquid trisodium citrate is added
And ascorbic acid, solution A is obtained, the molar concentration of ascorbic acid is 1 × 10 in solution A-5～1 × 10-1Mol/L, citric acid three
The molar concentration of sodium is 1 × 10-5～1 × 10-2mol/L；The mixed aqueous solution of sodium citrate and silver nitrate is prepared, B is designated as molten
Liquid, the concentration of silver nitrate is 1 × 10 in B solution-5～1 × 10-2Mol/L, the molar concentration of trisodium citrate is 1 × 10-5～1
×10-2mol/L；B solution is added dropwise in solution A, is reacted at room temperature, can when the ultraviolet of reaction system is measured
When seeing that near ir absorption peaks are less than or equal to 3000nm more than 600nm, stop Deca B solution, obtain various sizes of Nano silver piece
Solution.
4. the preparation method of the silver-gold-nano-piece based on epitaxially grown nucleocapsid structure according to claim 3, it is special
Levy and be：The average-size of the Nano silver piece in Nano silver piece solution after regulation is 30nm～5 μm.
5. the preparation method of the silver-gold-nano-piece based on epitaxially grown nucleocapsid structure according to claim 1, it is special
Levy and be：Described pH adjusting agent is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, phosphoric acid
Disodium hydrogen, dipotassium hydrogen phosphate or ammonia.
6. the preparation method of the silver-gold-nano-piece based on epitaxially grown nucleocapsid structure according to claim 1, it is special
Levy and be：Described surfactant is polyvinylpyrrolidone, polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer
Thing, dodecyl sodium sulfate or cetyl trimethylammonium bromide.
7. the preparation method of the silver-gold-nano-piece based on epitaxially grown nucleocapsid structure according to claim 1, it is special
Levy and be：Described reducing agent is ascorbic acid, oxammonium hydrochloride., formaldehyde, hydrazine hydrate or boron hydride.
8. the preparation side of the silver-gold-nano-piece based on epitaxially grown nucleocapsid structure in claim 1-7 described in any one
Silver-the gold-nano-piece of nucleocapsid structure obtained in method, it is characterised in that：Silver-the gold-nano-piece is by kernel portion and casing part structure
Into wherein kernel portion is Nano silver piece, and casing part is the gold nano layer gone out by epitaxial growth on Nano silver piece.
9. silver-the gold-nano-piece of the nucleocapsid structure described in claim 8 is in the Raman substrate for detecting organic molecule is prepared
Application.
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