CN116727678B - Gold nanoparticle with Yolk-Shell structure and preparation method thereof - Google Patents
Gold nanoparticle with Yolk-Shell structure and preparation method thereof Download PDFInfo
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 143
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 239000010931 gold Substances 0.000 title claims abstract description 129
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 129
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- PDHBRMFYIFYPQM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au].[Au] PDHBRMFYIFYPQM-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 32
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000005530 etching Methods 0.000 claims abstract description 18
- 230000035040 seed growth Effects 0.000 claims abstract description 16
- 239000002052 molecular layer Substances 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 45
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 36
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 26
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 21
- 101710134784 Agnoprotein Proteins 0.000 claims description 18
- 239000011668 ascorbic acid Substances 0.000 claims description 18
- 229960005070 ascorbic acid Drugs 0.000 claims description 18
- 235000010323 ascorbic acid Nutrition 0.000 claims description 18
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 239000004332 silver Substances 0.000 claims description 12
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 230000012010 growth Effects 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- -1 halogen ion Chemical class 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000007771 core particle Substances 0.000 claims description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- 239000002077 nanosphere Substances 0.000 claims description 3
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 230000003287 optical effect Effects 0.000 abstract description 3
- 239000000523 sample Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 44
- 239000000758 substrate Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229940089951 perfluorooctyl triethoxysilane Drugs 0.000 description 4
- 238000009832 plasma treatment Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000000861 blow drying Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 230000005672 electromagnetic field Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
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- 239000002244 precipitate Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 210000002969 egg yolk Anatomy 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000009022 nonlinear effect Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses gold nanoparticles with a Yolk-Shell structure and a preparation method thereof, belonging to the field of preparation of surface-enhanced Raman scattering materials, wherein a seed growth method is adopted to prepare a gold nanoparticle solution; adopting a halogen ion auxiliary method to obtain gold-silver bimetallic nanoparticles based on gold nanoparticle solution; a seed growth method is adopted to wrap a gold nano layer on the gold-silver bimetallic nano particles, so as to obtain the bimetallic nano particles with the structure of gold-silver-gold; and etching the gold-silver-gold bimetallic nano-particles with hydrogen peroxide to obtain gold nano-particles with a Yolk-Shell structure. The cavity structure of the gold nanoparticle can increase the specific surface area of the gold nanoparticle, so that the gold nanoparticle can anchor and adsorb more probe molecules and generate more active sites. The method can also provide a reaction place with a space limited domain for the nano gold particles, and obviously improve the performances of optical property, sensing property and the like of the nano gold, so that the nano gold has more excellent plasmon effect.
Description
Technical Field
The invention relates to the technical field of preparation of surface-enhanced Raman scattering materials, in particular to gold nanoparticles with a Yolk-Shell structure and a preparation method thereof.
Background
Surface Enhanced Raman Scattering (SERS) technology has attracted great attention and application in the fields of biological detection, environmental protection, chemical analysis, medical detection, etc. because of its excellent sensitivity, specificity and multiple encoding capability. On the basis, the three-dimensional SERS substrate has the natural advantages of strong adsorption capacity, good enhancement effect, high sensitivity and the like, and has important significance in the field of trace substance detection. However, the stability of SERS technology is somewhat dependent on the active substrate having surface enhancing capabilities, so preparing a substrate with high performance is critical to the utilization and development of SERS technology.
Due to the unique property of the gold nano material, the gold nano particles can strengthen local electric field in the range of a few nanometers on the particle surface caused by plasma resonance under the irradiation of visible light and near infrared light by several orders of magnitude compared with the incident electric field, so that the SERS effect is greatly improved, and the active base layer of the gold nano particles has the advantages of uniform particle size, good stability, strong absorption property and good fluorescence property, and is suitable for being used as an optical probe in biomedicine, biochemical marking and imaging analysis.
With the development and perfection of the nano material preparation technology, nano particles with different morphologies are successfully synthesized in experiments. The Yolk-Shell nano-structure material is a novel nano-material discovered in recent years, and has the structural characteristics that other particles are wrapped in an empty Shell, gaps exist between the two particles, and the nano-structure material is different from a core-Shell structure in that core nano-particles in the Yolk-Shell structure can move freely. The structure has the characteristics of low density, specific surface area, hollow interior and the like, can effectively weaken the covering effect of a Shell layer on active sites of metal particles, gold nano particles serving as Yolk in a Yolk-Shell structure are wrapped in a gold thin layer Shell, and the nano particles can freely roll in the Shell, and the active sites of the surface are completely exposed, so that the optical performance, sensing performance and the like of the nano gold can be remarkably improved, the nano gold has more excellent plasmon effect and good SERS characterization, and three-dimensional limitation and transmission of a light field are better realized, and the nano gold has great practical application significance.
Disclosure of Invention
The gold nanoparticle with the Yolk-Shell structure and the preparation method thereof provided by the invention can improve the performance of an SERS active substrate, and have the advantages of high SERS enhancement factor, high stability, strong anti-interference performance, high plasmon effect and the like.
The embodiment of the invention provides a preparation method of gold nanoparticles with a Yolk-Shell structure, which comprises the following steps: step S1, preparing gold nanoparticle solution by adopting a seed growth method; s2, adopting a halogen ion auxiliary method to obtain gold-silver bimetallic nanoparticles based on the gold nanoparticle solution; step S3, wrapping a gold nano layer for the gold-silver bimetallic nano particles by adopting a seed growth method to obtain the bimetallic nano particles with a gold-silver-gold structure; and S4, etching the gold-silver-gold bimetallic nanoparticles with hydrogen peroxide to obtain gold nanoparticles with a Yolk-Shell structure.
In one embodiment of the present invention, the method for preparing gold nanoparticles by using a seed growth method comprises the steps of:
step S11, adopting chloroauric acid HAuCl 4 Cetyl trimethylammonium bromide CTAB and sodium borohydride NaBH 4 Preparing seed liquid of gold nano particles;
step S12, using cetyl trimethyl ammonium bromide CTAB, sodium oleate NaOL and silver nitrate AgNO 3 Chloroauric acid HAuCl 4 Preparing a growth solution of gold nano particles by hydrochloric acid HCl and ascorbic acid AA;
and S13, adding the growth solution of the gold nanoparticles into the seed solution of the gold nanoparticles to prepare a gold nanoparticle solution.
In one embodiment of the present invention, in step S11, cetyltrimethylammonium bromide CTAB, chloroauric acid HAuCl 4 And sodium borohydride NaBH 4 The molar ratio of (2) is 800:1: 4-200: 1:8, wherein the final concentration of cetyltrimethylammonium bromide CTAB is 50-200 mM;
in step S12, cetyltrimethylammonium bromide CTAB, sodium oleate NaOL and silver nitrate AgNO 3 Chloroauric acid HAuCl 4 The molar ratio of HCl hydrochloride to ascorbic acid AA is 100:30:1:3:840:1 to 100:20:1:2:190:1, a step of; wherein, the final concentration of cetyl trimethyl ammonium bromide CTAB is 30-50 mM;
in the step S13, the volume ratio of the seed liquid of the gold nanoparticles to the growth liquid of the gold nanoparticles is 1:500-1:1000.
In one embodiment of the present invention, in step S1, the gold nanoparticles prepared by the seed growth method include gold nanorods, gold nanospheres, gold nanosatellites, and sizes of 10nm to 100nm.
In one embodiment of the invention, a halogen ion assisted method is adopted to obtain gold-silver bimetallic nanoparticles based on the gold nanoparticle solution, comprising:
step S21, sequentially adding silver nitrate AgNO into the gold nanoparticle solution 3 Hexadecyl radicalAnd reducing and coating a silver layer on the surface of the gold nanoparticle by trimethyl ammonium chloride CTAC and ascorbic acid AA to obtain the gold-silver bimetallic nanoparticle coated with the silver layer on the surface.
In one embodiment of the invention, in step S21, silver nitrate AgNO 3 The molar ratio of cetyltrimethylammonium chloride CTAC to ascorbic acid AA is 1:10:10 to 1:25:100, wherein the final concentration of the cetyl trimethyl ammonium chloride CATC is 5-20 mM.
In one embodiment of the present invention, a seed growth method is used to wrap a gold nano layer on the gold-silver bimetallic nanoparticle to obtain a gold-silver-gold bimetallic nanoparticle, which comprises:
step S31, adding chloroauric acid HAuCl after purifying the gold-silver bimetallic nano particles coated with the silver layer on the surface 4 Potassium iodide KI and ascorbic acid AA to prepare the gold-silver-gold bimetallic nanoparticle with a gold nano layer coated on the surface of the silver layer.
In one embodiment of the present invention, in step S31, chloroauric acid HAuCl 4 The molar ratio of potassium iodide KI to ascorbic acid AA is 1:1:10 to 1:4:100, wherein the final concentration of chloroauric acid is 0.025 mM-0.1 mM.
In one embodiment of the present invention, the gold-silver-gold bimetallic nanoparticle is etched with hydrogen peroxide to obtain a gold nanoparticle with a Yolk-Shell structure, which comprises:
hydrogen peroxide H is added into the gold-silver-gold bimetallic nano-particle 2 O 2 Etching for a preset time, and separating and purifying the nano particles after etching to obtain gold nano particles with a Yolk-Shell structure, wherein the hydrogen peroxide H 2 O 2 The concentration is 0.1-10%, and the etching preset time is at least 1min.
The embodiment of the invention also provides gold nanoparticles with a Yolk-Shell structure, which are prepared by the preparation method of the gold nanoparticles with the Yolk-Shell structure, wherein the gold nanoparticles with the Yolk-Shell structure are provided with concave hexahedral Shell layers and free gold nanoparticle inner cores, and the inner core particles are rod-shaped or spherical.
The gold nanoparticle with the Yolk-Shell structure and the preparation method thereof have the following beneficial effects:
1) The gold nanoparticle structure is adopted, and the active base layer of the gold nanoparticle is utilized, so that the nanoparticle has the advantages of uniform particle size and good stability;
2) After the Yolk-Shell structure is adopted for optimization, gold nano particles serving as Yolk are wrapped in a gold thin layer Shell, the nano particles can roll freely in the Shell, and active sites on the surface are completely exposed, so that the nano particles have more excellent plasmon effect and better SERS characterization, can enhance the electromagnetic field energy density in the sub-wavelength space scale of the metal surface, amplify the nonlinear effect amplitude, reduce the incident light intensity required by the nonlinear process, realize the generation of weak light nonlinear effect in the nano scale, and better realize the three-dimensional restriction and transmission of the light field.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a flow chart of a method for preparing gold nanoparticles with a Yolk-Shell structure according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of gold nanoparticles with a Yolk-Shell structure according to an embodiment of the present invention;
FIG. 3 is a TEM electron microscope image of gold nanoparticles of Yolk-Shell structure according to an embodiment of the present invention;
fig. 4 is a schematic diagram of FDTD electromagnetic field simulation of gold nanoparticles of Yolk-Shell structure according to an embodiment of the present invention.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
Fig. 1 is a flowchart of a preparation method of gold nanoparticles with a Yolk-Shell structure according to an embodiment of the present invention.
As shown in FIG. 1, the preparation method of the gold nanoparticle with the Yolk-Shell structure comprises the following steps:
step S1, preparing gold nanoparticle solution by adopting a seed growth method.
The gold nanoparticles prepared by the seed growth method comprise gold nanorods, gold nanospheres and gold nanosatellites, and the size of the gold nanosatellites is 10-100 nm.
As a specific embodiment, the method for preparing gold nanoparticles by using a seed growth method comprises the following steps:
step S11, adopting chloroauric acid HAuCl 4 Cetyl trimethylammonium bromide CTAB and sodium borohydride NaBH 4 And preparing a seed solution of gold nano particles.
In step S11, cetyltrimethylammonium bromide CTAB and chloroauric acid HAuCl 4 And sodium borohydride NaBH 4 The molar ratio of (2) is 800:1: 4-200: 1:8, wherein the final concentration of cetyltrimethylammonium bromide CTAB is 50-200 mM.
Step S12, using cetyl trimethyl ammonium bromide CTAB, sodium oleate NaOL and silver nitrate AgNO 3 Chloroauric acid HAuCl 4 And preparing the growth solution of gold nano particles by hydrochloric acid HCl and ascorbic acid AA.
In step S12, cetyltrimethylammonium bromide CTAB, sodium oleate NaOL and silver nitrate AgNO 3 Chloroauric acid HAuCl 4 The molar ratio of HCl hydrochloride to ascorbic acid AA is 100:30:1:3:840:1 to 100:20:1:2:190:1, a step of; wherein, the final concentration of cetyl trimethyl ammonium bromide CTAB is 30-50 mM.
Step S13, adding a growth solution of gold nanoparticles into the seed solution of gold nanoparticles to prepare a gold nanoparticle solution.
In the step S13, the volume ratio of the seed liquid of the gold nanoparticles to the growth liquid of the gold nanoparticles is 1:500-1:1000.
And S2, obtaining gold-silver bimetallic nanoparticles based on gold nanoparticle solution by adopting a halogen ion auxiliary method.
As a specific embodiment, silver nitrate AgNO is added into gold nanoparticle solution in sequence 3 And reducing and coating a silver layer on the surface of the gold nanoparticle by cetyl trimethyl ammonium chloride CTAC and ascorbic acid AA to obtain the gold-silver bimetallic nanoparticle coated with the silver layer on the surface.
Wherein, silver nitrate AgNO 3 The molar ratio of cetyltrimethylammonium chloride CTAC to ascorbic acid AA is 1:10:10 to 1:25:100, wherein the final concentration of the cetyl trimethyl ammonium chloride CATC is 5-20 mM.
And S3, coating a gold nano layer on the gold-silver bimetallic nano particles by adopting a seed growth method to obtain the bimetallic nano particles with the structure of gold-silver-gold.
As a specific embodiment, after purifying the gold-silver bimetallic nanoparticle coated with silver layer, adding chloroauric acid HAuCl 4 Potassium iodide KI and ascorbic acid AA to prepare the gold-silver-gold bimetallic nanoparticle with a gold nano layer coated on the surface of the silver layer.
Wherein, chloroauric acid HAuCl 4 The molar ratio of potassium iodide KI to ascorbic acid AA is 1:1:10 to 1:4:100, wherein the final concentration of chloroauric acid is 0.025 mM-0.1 mM.
And S4, etching the gold-silver-gold bimetallic nanoparticles with hydrogen peroxide to obtain gold nanoparticles with a Yolk-Shell structure.
As a specific embodiment, hydrogen peroxide H is added to gold-silver-gold bimetallic nanoparticles 2 O 2 Etching for a preset time, and separating and purifying the nano particles after etching to obtain gold nano particles with a Yolk-Shell structure.
Specifically, hydrogen peroxide H with the concentration of 0.1-10% is added into the gold-silver-gold bimetallic nano-particles obtained in the step S3 2 O 2 Etching for 1 min-several days, and separating and purifying the nano particles after etching to obtain the nano particles with Yolk-SheGold nanoparticles of ll structure.
Based on the preparation method, the gold nanoparticle with the Yolk-Shell structure with the concave hexahedral Shell layer and the free gold nanoparticle inner core can be obtained, and the inner core particle is rod-shaped or spherical.
As shown in fig. 2, 3 and 4, the structure of gold nanoparticles of the Yolk-Shell structure, TEM electron microscope images, and FDTD electromagnetic field simulation images of gold nanoparticles of the Yolk-Shell structure are shown.
The preparation method of gold nanoparticles of the Yolk-Shell structure of the present invention is described below by way of three specific examples.
Example 1
Take the application of the gold nanoparticle surface enhanced Raman scattering substrate based on the Yolk-Shell structure in the detection of trace food additives (such as rhodamine 6G and the like) as an example.
S1: 5mL of HAuCl containing 0.005mmol 4 A mixed solution was prepared from the solution of (C) and 2.5mL of a CTAB solution containing 0.5 mmol. 0.01mmol of NaBH was added 4 Stirring for 2min, standing at room temperature, and aging for 2h to obtain gold seed solution. 25mmo1 CTAB and 7.5mmo NaOL solids were dissolved in 250mL deionized water, and 0.25mmo AgNO was added to the mixture in sequence 3 ,0.75mmol HAuCl 4 210mmol of HCl,0.25mmol of AA, and 1mL of gold seed solution was added thereto after the total volume had reached 500mL by adding water, and the mixture was allowed to stand for 12 hours. The resulting solution was centrifuged and dispersed in 500mL deionized water.
S2: to the resulting solution was added sequentially 1mmol of AgNO 3 10mmol CTAC, 10mmol AA, and stirred at 65℃for 1h. The pellet was resuspended in 500mL deionized water by centrifugation.
S3: will 0.0125mmol HAuCl 4 To the above solution, 0.0125KI and 0.125mmol AA were added, and after stirring for 20min, the mixture was centrifuged to disperse to 5mL,1mM CTAB solution.
S4: to the above solution was added 0.5 mmole of H 2 O 2 Etching for 45min, centrifuging, and collecting precipitate.
S5: placing the silicon wafer subjected to oxygen plasma treatment and 1H, 2H-perfluorooctyl triethoxysilane in a vacuum vessel, and keeping the vacuum state for 1h. 2uL of the nano colloid obtained by S4 is dripped on a silanized silicon wafer and placed in a constant temperature box and a constant humidity box at 37 ℃ for standing for 72 hours.
S6: immersing the substrate obtained in the step S4 into rhodamine 6G aqueous solution for 5min, taking out the substrate and then taking out the substrate N 2 Blow-drying, and performing SERS detection.
Example 2
S1: 5mL of HAuCl containing 0.0025mmol 4 A mixed solution was prepared from the solution of (C) and 2.5mL of a CTAB solution containing 1 mmol. Add NaBH containing 0.0075mmol 4 Stirring for 2min, standing at room temperature, and aging for 2h to obtain gold seed solution. 20mmo1 CTAB and 6mmo NaOL solids were dissolved in 250mL deionized water, and 0.2mmo AgNO was added to the mixture in sequence 3 ,0.5mmol HAuCl 4 103mmol of HCl,0.2mmol of AA, and water were added to a total volume of 500mL, and then 0.75mL of gold seed solution was added thereto and allowed to stand for 12 hours. The resulting solution was centrifuged and dispersed in 500mL deionized water.
S2: to the resulting solution was added 0.5mmol of AgNO in sequence 3 5mmol CTAC, 14.25mmol AA, and stirred at 65℃for 1h. The pellet was resuspended in 500mL deionized water by centrifugation.
S3: will be 0.025mmol of HAuCl 4 To the above solution, 0.05mmol KI and 1.25mmol AA were added, and after stirring for 20min, the mixture was centrifuged to disperse to a 5mL,0.5mM CTAB solution.
S4: adding 0.05 mmole of H to the above solution 2 O 2 Etching for 3h, centrifuging, and collecting precipitate.
S5: placing the silicon wafer subjected to oxygen plasma treatment and 1H, 2H-perfluorooctyl triethoxysilane in a vacuum vessel, and keeping the vacuum state for 1h. 2uL of the nano colloid obtained by S4 is dripped on a silanized silicon wafer and placed in a constant temperature box and a constant humidity box at 37 ℃ for standing for 72 hours.
S6: immersing the substrate obtained in the step S4 into rhodamine 6G aqueous solution for 5min, taking out the substrate and then taking out the substrate N 2 Blow-drying, and performing SERS detection.
Example 3
S1: 5mL of HAuCl containing 0.00125mmol 4 A mixed solution was prepared from the solution of (C) and 2.5mL of a CTAB solution containing 2 mmol. Adding NaBH of 0.005mmol 4 Stirring for 2min, and cooling to room temperatureStanding and aging for 2 hours to obtain the gold seed solution. 15mmo1 CTAB and 3mmo NaOL solids were dissolved in 250mL deionized water, and 0.15mmo AgNO was added to the mixture in sequence 3 ,0.3mmol HAuCl 4 28.5mmol of HCl and 0.15mmol of AA, water was added to make the total volume 500mL, and then 0.5mL of gold seed solution was added and allowed to stand for 12 hours. The resulting solution was centrifuged and dispersed in 500mL deionized water.
S2: to the resulting solution was added 0.25mmol of AgNO in sequence 3 2.5mmol CTAC, 10mmol AA, and stirred at 65℃for 1h. The pellet was resuspended in 500mL deionized water by centrifugation.
S3: will 0.05mmol of HAuCl 4 To the above solution, 0.2mmol KI and 5mmol AA were added, and after stirring for 20min, the mixture was centrifuged to disperse to 5mL of a 0.2mM CTAB solution.
S2: placing the silicon wafer subjected to oxygen plasma treatment and 1H, 2H-perfluorooctyl triethoxysilane in a vacuum vessel, and keeping the vacuum state for 1h. The 10uL of the nano colloid solution obtained by S1 is dripped on a silanized silicon wafer and placed in a constant temperature box and a constant humidity box at 37 ℃ for standing for 72 hours.
S3: the substrate obtained in S2 was treated with hydrogen and argon plasma with a chamber vacuum of 0.5torr, hydrogen: argon is 1:4, the treatment frequency is 100kHz, the treatment power is 100W, and the time is 10min.
S4: to the above solution was added 0.025mmol H 2 O 2 Etching for 48h, centrifuging, and collecting precipitate.
S5: placing the silicon wafer subjected to oxygen plasma treatment and 1H, 2H-perfluorooctyl triethoxysilane in a vacuum vessel, and keeping the vacuum state for 1h. 2uL of the nano colloid obtained by S4 is dripped on a silanized silicon wafer and placed in a constant temperature box and a constant humidity box at 37 ℃ for standing for 72 hours.
S6: immersing the substrate obtained in the step S4 into rhodamine 6G aqueous solution for 5min, taking out the substrate and then taking out the substrate N 2 Blow-drying, and performing SERS detection.
According to the preparation method of gold nanoparticles with the Yolk-Shell structure, provided by the embodiment of the invention, the cavity structure of the gold nanoparticles with the Yolk-Shell structure can increase the specific surface area of the gold nanoparticles, so that the gold nanoparticles can anchor and adsorb more probe molecules and generate more active sites. In addition, the Yolk-Shell structure can provide a reaction place of a space limited domain for the nano gold particles, and the performances of the nano gold such as optics and sensing are obviously improved, so that the nano gold has more excellent plasmon effect.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or N embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "N" means at least two, for example, two, three, etc., unless specifically defined otherwise.
Any process or method descriptions in flow charts or otherwise described herein may be understood as representing modules, segments, or portions of code which include one or more executable instructions for implementing specific logical functions or steps of the process, and additional implementations are included within the scope of the preferred embodiment of the present invention in which functions may be executed out of order from that shown or discussed, including substantially concurrently or in reverse order from that shown or discussed, depending on the functionality involved, as would be understood by those reasonably skilled in the art of the embodiments of the present invention.
Claims (2)
1. The preparation method of gold nano particles with a Yolk-Shell structure is characterized by comprising the following steps of:
step S1, preparing gold nanoparticle solution by adopting a seed growth method;
s2, adopting a halogen ion auxiliary method to obtain gold-silver bimetallic nanoparticles based on the gold nanoparticle solution;
step S3, wrapping a gold nano layer for the gold-silver bimetallic nano particles by adopting a seed growth method to obtain the bimetallic nano particles with a gold-silver-gold structure;
step S4, etching the gold-silver-gold bimetallic nanoparticles with hydrogen peroxide to obtain gold nanoparticles with a Yolk-Shell structure;
the method for preparing gold nanoparticles by adopting the seed growth method comprises the following steps:
step S11, adopting chloroauric acid HAuCl 4 Cetyl trimethylammonium bromide CTAB and sodium borohydride NaBH 4 Preparing seed liquid of gold nano particles;
step S12, using cetyl trimethyl ammonium bromide CTAB, sodium oleate NaOL and silver nitrate AgNO 3 Chloroauric acid HAuCl 4 Preparing a growth solution of gold nano particles by hydrochloric acid HCl and ascorbic acid AA;
step S13, adding a growth solution of the gold nanoparticles into a seed solution of the gold nanoparticles to prepare a gold nanoparticle solution;
in step S11, cetyltrimethylammonium bromide CTAB and chloroauric acid HAuCl 4 And sodium borohydride NaBH 4 The molar ratio of (2) is 800:1: 4-200: 1:8, wherein the final concentration of cetyltrimethylammonium bromide CTAB is 50-200 mM;
in step S12, cetyltrimethylammonium bromide CTAB, sodium oleate NaOL and silver nitrate AgNO 3 Chloroauric acid HAuCl 4 The molar ratio of HCl hydrochloride to ascorbic acid AA is 100:30:1:3:840:1 to 100:20:1:2:190:1, a step of; wherein, the final concentration of cetyl trimethyl ammonium bromide CTAB is 30-50 mM;
in the step S13, the volume ratio of the seed liquid of the gold nano particles to the growth liquid of the gold nano particles is 1:500-1:1000;
in the step S1, the gold nanoparticles prepared by adopting a seed growth method comprise gold nanorods, gold nanospheres and gold nanosatellites, wherein the size of the gold nanosatellites is 10-100 nm;
the gold-silver bimetallic nanoparticle based on the gold nanoparticle solution is obtained by adopting a halogen ion auxiliary method, and the method comprises the following steps:
step S21, sequentially adding silver nitrate AgNO into the gold nanoparticle solution 3 Reducing and coating a silver layer on the surface of the gold nano-particle by cetyl trimethyl ammonium chloride CTAC and ascorbic acid AA to obtain a gold-silver bimetallic nano-particle coated with the silver layer on the surface;
in step S21, silver nitrate AgNO 3 The molar ratio of cetyltrimethylammonium chloride CTAC to ascorbic acid AA is 1:10:10 to 1:25:100, wherein the final concentration of the cetyl trimethyl ammonium chloride CATC is 5-20 mM;
a seed growth method is adopted to wrap a gold nano layer on the gold-silver bimetallic nano particles to obtain the bimetallic nano particles with the structure of gold-silver-gold, which comprises the following steps:
step S31, adding chloroauric acid HAuCl after purifying the gold-silver bimetallic nano particles coated with the silver layer on the surface 4 Potassium iodide KI and ascorbic acid AA to prepare gold-silver-gold bimetallic nanoparticles with a gold nano layer coated on the surface of a silver layer;
in step S31, chloroauric acid HAuCl 4 The molar ratio of potassium iodide KI to ascorbic acid AA is 1:1:10 to 1:4:100, wherein the final concentration of chloroauric acid is 0.025 mM-0.1 mM;
etching the gold-silver-gold bimetallic nanoparticle with hydrogen peroxide to obtain a gold nanoparticle with a Yolk-Shell structure, wherein the gold nanoparticle comprises the following components:
hydrogen peroxide H is added into the gold-silver-gold bimetallic nano-particle 2 O 2 Etching for a preset time, and separating and purifying the nano particles after etching to obtain gold nano particles with a Yolk-Shell structure; wherein the hydrogen peroxide solution H 2 O 2 The concentration is 0.1-10%, and the etching preset time is at least 1min.
2. A gold nanoparticle with a Yolk-Shell structure, which is prepared by the preparation method of the gold nanoparticle with the Yolk-Shell structure as claimed in claim 1, is characterized in that,
the gold nanoparticles with the Yolk-Shell structure are provided with concave hexahedral shells and free gold nanoparticle cores, and the core particles are rod-shaped or spherical.
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