CN116475425A - Method for synthesizing gold/silver core-shell structure nano particles - Google Patents
Method for synthesizing gold/silver core-shell structure nano particles Download PDFInfo
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- CN116475425A CN116475425A CN202310381729.7A CN202310381729A CN116475425A CN 116475425 A CN116475425 A CN 116475425A CN 202310381729 A CN202310381729 A CN 202310381729A CN 116475425 A CN116475425 A CN 116475425A
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 41
- 239000010931 gold Substances 0.000 title claims abstract description 41
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 38
- 239000004332 silver Substances 0.000 title claims abstract description 38
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000011258 core-shell material Substances 0.000 title claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 8
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims abstract description 8
- -1 acetic acid-chlorine-gold Chemical compound 0.000 claims abstract description 8
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 6
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 4
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000007865 diluting Methods 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 229920000858 Cyclodextrin Polymers 0.000 claims description 17
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
- 239000001116 FEMA 4028 Substances 0.000 claims description 14
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 14
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 14
- 229960004853 betadex Drugs 0.000 claims description 14
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 claims description 12
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 claims description 12
- 229940043377 alpha-cyclodextrin Drugs 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- VRYGRLBNIVQXMY-UHFFFAOYSA-M sodium;acetic acid;chloride Chemical compound [Na+].[Cl-].CC(O)=O VRYGRLBNIVQXMY-UHFFFAOYSA-M 0.000 claims description 4
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 6
- 150000001875 compounds Chemical group 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 description 13
- 239000002086 nanomaterial Substances 0.000 description 11
- 239000013078 crystal Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000002343 gold Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- JAJIPIAHCFBEPI-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O JAJIPIAHCFBEPI-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000000441 X-ray spectroscopy Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical group [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000006467 substitution reaction 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
- B22F1/17—Metallic particles coated with metal
-
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a method for synthesizing gold/silver core-shell structured nano particles, which comprises the following steps: s01, preparing silver sol and diluting with water to obtain silver sol solution, wherein the volume ratio of the silver sol to the water is 1:05 to 1:2; s02, adding sodium dodecyl sulfate into the silver sol solution, wherein the mass ratio of the sodium dodecyl sulfate to the silver sol is 1:300-1:1000; s03, adding an acetic acid-chlorine-gold complex solution into the product in the step S02 according to the volume ratio of 1:200-1:50 at the temperature of 30-80 ℃; s04, adding ascorbic acid into the product obtained in the step S03 according to the mass ratio of 1:2000-1:200, and stirring for 2-20 min; s05, standing and cooling the solution in the step S04 to obtain noble metal sol. The method solves the problems that the gold shell silver core nano particles generated in the prior art all have compound forms and are not complete gold and silver simple substance forms.
Description
Technical Field
The invention relates to a method for synthesizing gold/silver core-shell structure nano particles, belonging to the field of nano materials.
Background
Gold and silver nano particles belong to metal-based synthetic nano materials of synthetic nano materials, have the chemical characteristics of noble metals and the performances of nano particles, have special properties and functions, and are widely applied to the fields of catalysts, sensing elements, optical devices, biomedicine and the like. At present, colloidal gold (gold nano) is rapidly applied and developed in the fields of immune technology, food safety, chemical catalysis, surface enhancement and the like. The gold nanoparticles are uniform and stable, and the silver nanoparticles have the advantages of good optical properties, low cost and the like. The gold shell nano material with the silver core coated by the synthetic gold can combine the advantages of the gold shell nano material and the silver core, and form application advantages with the advantage of low cost.
The synthesis of the gold-shell silver-core nano-particles has great technical difficulty, the firm attachment, uniform growth and uniform encapsulation of gold atom clusters on the silver-core nano-particles are required to be completed in a microscopic nano-size, and good dispersion and stability are also required to be obtained. So far, successful cases are not many, and meanwhile, reported cases have problems which are not thoroughly solved in technology.
In the current limited reports on the synthesis of gold-shell silver-core nano particles, generally, based on the synthesis of silver nano particles, tetrachloro-alloy acid is added, and gold is reduced by a displacement reaction or by adding a reducing agent. But the synthesized nano particles are unstable and easy to agglomerate, and gold is loosely adhered to the surface of the silver core. Meanwhile, silver ions and chloride ions rapidly generate silver chloride precipitates, and the silver nuclei surface layer is blocked for affinity and package with gold. Tetraiodo alloy acid is also used to replace tetrachloro alloy acid, but the effect of both is close and the synthesis effect is not ideal. The nano particles obtained by the method are detected under a transmission electron microscope, and have compound forms but not complete gold and silver simple substance forms, so that the gold-silver core composite nano particles are limited in application and have no effective application in the fields of immune technology, food safety, chemical catalysis and the like.
Disclosure of Invention
The invention aims to solve the technical problems that: a method for synthesizing gold/silver core-shell structured nanoparticles is provided to overcome the above-mentioned problems of the prior art.
The technical scheme of the invention is as follows: a method for synthesizing gold/silver core-shell structured nano particles, comprising the following steps:
s01, preparing silver sol and diluting with water to obtain silver sol solution, wherein the volume ratio of the silver sol to the water is 1:05 to 1:2;
s02, adding sodium dodecyl sulfate into the silver sol solution, wherein the mass ratio of the sodium dodecyl sulfate to the silver sol is 1:300-1:1000;
s03, adding an acetic acid-chlorine-gold complex solution into the product in the step S02 according to the volume ratio of 1:200-1:50 at the temperature of 30-80 ℃;
s04, adding ascorbic acid into the product obtained in the step S03 according to the mass ratio of 1:2000-1:200, and stirring for 2-20 min;
s05, standing and cooling the solution in the step S04 to obtain noble metal sol;
wherein, the preparation method of the acetic acid-chlorine-gold complex solution comprises the following steps: preparing an acetic acid solution, and dissolving sodium chloride in the acetic acid solution to obtain a sodium chloride acetic acid solution; gold is added into sodium chloride acetic acid solution at 60-95 ℃ and nitric acid is added until gold is completely dissolved, thus obtaining the 'acetic acid-chlorine-gold' complex solution.
Preferably, the method for preparing silver sol in the step S01 includes the following steps:
s01-1, dissolving alpha-cyclodextrin or beta-cyclodextrin into water according to a mass ratio of 1:500-1:50 to obtain an alpha-cyclodextrin solution or a beta-cyclodextrin solution; dissolving silver nitrate into water according to a mass ratio of 1:6000-1:1000 to obtain a silver nitrate solution;
s01-2, adding n-butanol into the alpha-cyclodextrin solution or the beta-cyclodextrin solution according to the volume ratio of 1:100-1:10, and adding ethanol into the alpha-cyclodextrin solution or the beta-cyclodextrin solution according to the volume ratio of 1:100-1:10;
s01-3, adding silver nitrate solution prepared in the step S01-1 into the product of the step S01-2 according to the volume ratio of 1:250-1:25 at the temperature of 30-90 ℃;
s01-4, 1-10 min later, dripping NaOH solution into the product of the step S01-3 to adjust the PH to 10-12, and continuously stirring for 10-30 min.
Preferably, the reaction conditions of step S01-3 further comprise: stirring was vigorously carried out in a water bath.
The beneficial effects of the invention are as follows: compared with the prior art, the invention has the following advantages: according to the invention, the silver nano particles are prepared by reduction of alpha-cyclodextrin or beta-cyclodextrin, meanwhile, the alpha-cyclodextrin or the beta-cyclodextrin has a special adsorption effect on gold, under the condition of regulating polarity, the surface tension environment of a cyclodextrin solution is favorable for the growth of gold on the surface layer of silver cores, the affinity and adhesion of two metals are obtained under the micro environment, the gold is firmly adhered on the surface layer of the silver cores, and a sol system is uniformly dispersed; gold is dissolved in an unconventional mode to be used as a gold source, the novel gold complex has excellent affinity with silver cores in cyclodextrin solution, the effect in cyclodextrin solution is good, gold shells uniformly grow on the surface layers of the silver cores, the coating is uniform and firm, and compared with gold salt reagents such as tetrachloro-alloy acid, the effect of reducing the carry-in of halides in the synthesis process is better; the composite nano particles are formed by simple substance forms of gold and silver, and the purity is high. Providing good conditions for the application of the composite nano material.
Drawings
FIG. 1 is a graph showing the diffraction results of crystals of gold complexes prepared in accordance with the present invention;
FIG. 2 is a graph showing the diffraction results of another crystal of the gold complex prepared according to the present invention;
FIG. 3 is a graph showing the diffraction results of another crystal of the gold complex prepared according to the present invention;
FIG. 4 is a graph showing the diffraction results of another crystal of the gold complex prepared according to the present invention;
FIG. 5 is a TEM image of the gold-shell silver-core composite nanoparticle prepared by the invention at different multiplying powers;
FIG. 6 is a TEM image of particles (a) of the gold-shell silver-core composite nanomaterial made in accordance with the present invention;
FIG. 7 is a TEM image of particles (b) of the gold-shell silver-core composite nanomaterial made in accordance with the present invention;
FIG. 8 is a graph of EDS results analysis of the particles of FIG. 6 (a);
FIG. 9 is a graph of EDS results analysis of the particles of FIG. 7 (b);
FIG. 10 is a graphical representation of silver sol prepared from beta-cyclodextrin made in accordance with the present invention;
FIG. 11 is a physical diagram of the gold-shell silver-core composite nanomaterial made by the invention;
fig. 12 is another physical diagram of the gold-shell silver-core composite nanomaterial made by the present invention.
Detailed Description
In order to better understand the above technical solution, the following detailed description will explain the above technical solution in conjunction with specific embodiments.
Implementation example 1:
1) Dissolving alpha-cyclodextrin or beta-cyclodextrin in water according to a mass ratio of 1:500-1:50; silver nitrate is dissolved in water according to the mass ratio of 1:6000-1:1000.
2) 200ml of alpha-cyclodextrin solution or beta-cyclodextrin solution is taken, n-butanol is added according to the volume ratio of 1:100-1:10, ethanol is added according to the volume ratio of 1:100-1:10, the mixture is poured into a 250ml three-neck flask, 1-10 ml of prepared silver nitrate solution is added into the three-neck flask, and the mixture is vigorously stirred under a water bath at 30-90 ℃.
3) After 1-10 min, naOH solution (1.0 mol/L) is added dropwise to adjust the PH value to 10-12. Stirring is continued for 10-30 min, and yellow silver sol is obtained.
4) Acetic acid was dissolved in water at a volume ratio of 1:50 to 1:5, and sodium chloride was further dissolved in the solution at a mass ratio of 1:300 to 1:30, 100ml of the solution was taken and added to a 400ml beaker. Adding gold into the solution according to the mass ratio of 1:1000-1:100, heating to 60-95 ℃, dripping nitric acid until the gold is completely dissolved, and stopping dripping. To prepare the acetic acid-chlorine-gold complex solution.
5) And 3) adding water into the silver sol prepared in the step 3) to dilute, wherein the volume ratio of the silver sol to the water is 1:0.5-1:2. Adding sodium dodecyl sulfate into the sol, wherein the mass ratio of the sodium dodecyl sulfate to the silver sol is 1:300-1:1000, taking 200ml, and placing into a three-neck flask.
6) Heating to 30-80 ℃, adding the acetic acid-chlorine-gold complex solution prepared in the step 4) into the mixture according to the volume ratio of 1:200-1:50, uniformly mixing the mixture, adding ascorbic acid according to the mass ratio of 1:2000-1:200 after 1-5 minutes, and stirring the mixture for 2-20 minutes.
7) And taking out the three-neck flask, standing and cooling. Pouring out the noble metal sol, placing the noble metal sol into a conical flask, and placing the conical flask into a refrigerator for preservation at 4 ℃.
Experimental results:
1) The silver sol prepared by the beta-cyclodextrin prepared by the method is shown in figure 10;
2) The gold-shell silver-core nanoparticle real object prepared by the method is shown in fig. 11 and 12;
3) The method for dissolving gold by using acetic acid and sodium chloride as ligands and nitric acid as an oxidant is an unconventional method, and the method has a rapid and good gold dissolving effect, is a typical complex with a clear structure, is a complex different from tetrachloro-alloy acid, and forms coordination with gold for the first time. The crystal diffraction data are shown in figures 1-4; the diffraction results show that: the crystal is highly regular, and gold forms good coordination with acetate and chlorine; is a different complex from the tetrachloro-alloy acid.
4) The prepared gold-shell silver-core nano-particles can be kept uniform and stable for 100 days at 4 ℃ without agglomeration;
5) TEM detection
The obtained gold-shell silver-core nanoparticle was subjected to transmission electron microscope scanning (TEM) by the institute of geochemistry, guiyang, china academy of sciences, and the result is shown in FIG. 5.
As can be seen from fig. 5, the composite nanomaterial prepared by the method has good dispersion degree, uniform dispersion and good crystal morphology.
As can be seen from fig. 6 and 7, after further scanning the composite nanoparticle, the nanoparticle exhibited a typical crystal morphology, showing that gold clusters grew well on the silver core and formed a well crystallized elemental morphology. The composite nano particles have two contrast levels with obvious depth, which are shown under TEM scanning due to the large difference of gold and silver atomic weight. The composite nanometer grain diameter is 20-40nm, the crystallization is good, and the outer layer is uniformly wrapped.
6) X-ray energy spectrum analysis (EDS)
The nanoparticles of fig. 6 and 7 were subjected to X-ray spectroscopy (EDS) and the composition is shown in table 1 and fig. 8 to 9.
TABLE 1 analysis of ingredients
Analysis of the composition of the composite (Table 1) shows that the silver core mass percent is about 75-80% and the gold shell mass percent is about 15-20%.
The foregoing is a further detailed description of the invention in connection with the preferred embodiments, and it is not intended that the invention be limited to the specific embodiments described. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.
Claims (3)
1. The method for synthesizing the gold/silver core-shell structured nano-particles is characterized by comprising the following steps of:
s01, preparing silver sol and diluting with water to obtain silver sol solution, wherein the volume ratio of the silver sol to the water is 1:05 to 1:2;
s02, adding sodium dodecyl sulfate into the silver sol solution, wherein the mass ratio of the sodium dodecyl sulfate to the silver sol is 1:300-1:1000;
s03, adding an acetic acid-chlorine-gold complex solution into the product in the step S02 according to the volume ratio of 1:200-1:50 at the temperature of 30-80 ℃;
s04, adding ascorbic acid into the product obtained in the step S03 according to the mass ratio of 1:2000-1:200, and stirring for 2-20 min;
s05, standing and cooling the solution in the step S04 to obtain noble metal sol;
wherein, the preparation method of the acetic acid-chlorine-gold complex solution comprises the following steps: preparing an acetic acid solution, and dissolving sodium chloride in the acetic acid solution to obtain a sodium chloride acetic acid solution; gold is added into sodium chloride acetic acid solution at 60-95 ℃ and nitric acid is added until gold is completely dissolved, thus obtaining the 'acetic acid-chlorine-gold' complex solution.
2. The method for synthesizing gold/silver core-shell structured nano-particles according to claim 1, wherein the method for preparing silver sol in the step S01 comprises the following steps:
s01-1, dissolving alpha-cyclodextrin or beta-cyclodextrin into water according to a mass ratio of 1:500-1:50 to obtain an alpha-cyclodextrin solution or a beta-cyclodextrin solution; dissolving silver nitrate into water according to a mass ratio of 1:6000-1:1000 to obtain a silver nitrate solution;
s01-2, adding n-butanol into the alpha-cyclodextrin solution or the beta-cyclodextrin solution according to the volume ratio of 1:100-1:10, and adding ethanol into the alpha-cyclodextrin solution or the beta-cyclodextrin solution according to the volume ratio of 1:100-1:10; s01-3, adding silver nitrate solution prepared in the step S01-1 into the product of the step S01-2 according to the volume ratio of 1:250-1:25 at the temperature of 30-90 ℃;
s01-4, 1-10 min later, dripping NaOH solution into the product of the step S01-3 to adjust the PH to 10-12, and continuously stirring for 10-30 min.
3. The method for synthesizing gold/silver core-shell structured nanoparticles according to claim 2, wherein the reaction conditions of step S01-3 further comprise: stirring was vigorously carried out in a water bath.
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