CN114888300A - AuAgCu three-component alloy nano-cluster with controllable atomic number and size and preparation method thereof - Google Patents
AuAgCu three-component alloy nano-cluster with controllable atomic number and size and preparation method thereof Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000003446 ligand Substances 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 20
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 10
- 229910052737 gold Inorganic materials 0.000 claims abstract description 7
- 229910052709 silver Inorganic materials 0.000 claims abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 5
- 239000011593 sulfur Substances 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 239000010931 gold Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 8
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- -1 silver tetrafluoroborate Chemical compound 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000010944 silver (metal) Substances 0.000 claims description 5
- ADJJLNODXLXTIH-UHFFFAOYSA-N adamantane-1-thiol Chemical compound C1C(C2)CC3CC2CC1(S)C3 ADJJLNODXLXTIH-UHFFFAOYSA-N 0.000 claims description 4
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 4
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 claims description 4
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 4
- 229940071536 silver acetate Drugs 0.000 claims description 4
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 claims description 4
- PPWNCLVNXGCGAF-UHFFFAOYSA-N 3,3-dimethylbut-1-yne Chemical group CC(C)(C)C#C PPWNCLVNXGCGAF-UHFFFAOYSA-N 0.000 claims description 3
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 3
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 claims description 3
- CLDWGXZGFUNWKB-UHFFFAOYSA-M silver;benzoate Chemical compound [Ag+].[O-]C(=O)C1=CC=CC=C1 CLDWGXZGFUNWKB-UHFFFAOYSA-M 0.000 claims description 3
- 229940080262 sodium tetrachloroaurate Drugs 0.000 claims description 3
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 3
- DHBXNPKRAUYBTH-UHFFFAOYSA-N 1,1-ethanedithiol Chemical compound CC(S)S DHBXNPKRAUYBTH-UHFFFAOYSA-N 0.000 claims description 2
- AZJXVWFSXFKQSF-UHFFFAOYSA-N 2,2-dimethyl-1-phenylpropane-1-thiol Chemical compound CC(C)(C)C(S)C1=CC=CC=C1 AZJXVWFSXFKQSF-UHFFFAOYSA-N 0.000 claims description 2
- ZMRFRBHYXOQLDK-UHFFFAOYSA-N 2-phenylethanethiol Chemical compound SCCC1=CC=CC=C1 ZMRFRBHYXOQLDK-UHFFFAOYSA-N 0.000 claims description 2
- USCSRAJGJYMJFZ-UHFFFAOYSA-N 3-methyl-1-butyne Chemical compound CC(C)C#C USCSRAJGJYMJFZ-UHFFFAOYSA-N 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- 150000004677 hydrates Chemical class 0.000 claims description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 claims 2
- 229910021590 Copper(II) bromide Inorganic materials 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 4
- 229910001092 metal group alloy Inorganic materials 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- UKHWJBVVWVYFEY-UHFFFAOYSA-N silver;hydrate Chemical compound O.[Ag+] UKHWJBVVWVYFEY-UHFFFAOYSA-N 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- 229910002058 ternary alloy Inorganic materials 0.000 description 1
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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
- B22F1/0553—Complex form nanoparticles, e.g. prism, pyramid, octahedron
-
- 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
- B22F1/06—Metallic powder characterised by the shape of the particles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses an AuAgCu three-component alloy nano-cluster with controllable atomic number and size and a preparation method thereof, belonging to the technical field of metal alloy nano-clusters. Firstly, dissolving an Au precursor, an Ag precursor and a Cu precursor in a certain proportion in a mixed solution of water and toluene, stirring for a period of time, then adding a nitrogen-containing ligand, a sulfur-containing ligand and an alkynyl-containing ligand for reaction, adding sodium borohydride for reduction after the reaction for a period of time to obtain zero-valent AuAgCu alloy nano particles, and finally obtaining the AuAgCu three-component alloy nano cluster with controllable atomic number and size along with the extension of the reaction time. And obtaining the AuAgCu alloy nanoclusters with accurate atomic number and different sizes by adjusting the atomic ratio of Au, Ag and Cu and the ratio of ligands. The preparation method has universality and simple operation, and AuAgCu alloy nanoclusters with different sizes are obtained by changing the atomic ratio of Au, Ag and Cu.
Description
Technical Field
The invention belongs to the technical field of metal alloy nanoclusters, and particularly relates to an AuAgCu three-component alloy nanocluster with controllable atomic number and size and a preparation method thereof.
Background
In recent years, the preparation of metal nano materials is attracting more and more attention. Metal nanoclusters generally refer to metal particles having a size of less than 3nm and having a precise number of metal atoms and ligands, a precise crystal structure, generally a core-shell structure composed of metal and ligands. The core mainly comprises a metal bond, the ligand and the metal are coordinated to form a shell layer, and the physical and chemical properties of the metal nanocluster can be controlled by controlling factors such as size, morphology, composition or functional groups. The metal nanoclusters have great application potential in the aspects of catalysis, sensing, biological imaging, drug delivery, cancer treatment and the like, so that the preparation of the metal nanoclusters containing accurate atom numbers and rich in different surface functional groups has important significance.
Currently, a series of binary alloy nanoclusters are synthesized. For example, Zhengnan peak group successfully synthesized Au using cationic ligand 24 Ag 20 Alloy nanoclusters and their crystal structure (J.Am.chem.Soc.,2015,137,4324-4327) are obtained. However, the steps of the current method for synthesizing many metal nanoclusters are complicated, and the operation is complex, so that the effective synthesis of the ternary alloy nanoclusters with different sizes and accurate atomic numbers is still a challenge.
Disclosure of Invention
In view of the above, the present invention aims to provide an AuAgCu three-component alloy nanocluster with controllable atomic number and size and a preparation method thereof, wherein the AuAgCu three-component alloy nanocluster with controllable atomic number and size is synthesized by a one-step method, the method is simple, convenient and feasible, and convenient to operate, and the method can directly prepare the heterogeneous AuAgCu alloy nanocluster with controllable atomic number and size in the same reaction system by changing the precursor ratios of Au, Ag and Cu, the ligand types, the addition amount of a reducing agent, the reaction temperature and the reaction time.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of an AuAgCu three-component alloy nano cluster with controllable atomic number and size mainly comprises the following steps:
(1) dissolving an Au precursor, an Ag precursor and a Cu precursor in toluene or a mixed solution of water and toluene to obtain a reaction system 1;
(2) adding a phase transfer reagent into the reaction system 1, and stirring for 5-180 minutes at 3-85 ℃ to obtain a reaction system 2;
(3) adding one or more of a nitrogen-containing ligand, a sulfur-containing ligand and an alkynyl-containing ligand into the reaction system 2, and stirring for 0.1-24 hours at 5-70 ℃ to obtain a reaction system 3;
(4) adding sodium borohydride into the reaction system 3, and stirring and reacting for 0.1-144 hours at 5-90 ℃ to obtain a product;
(5) and (4) separating, spin-drying, washing and extracting the product obtained in the step (4) to obtain the AuAgCu three-component alloy nanocluster with controllable atom number and size.
Based on the technical scheme, further, the molar ratio of the Au precursor to the Ag precursor to the Cu precursor in the step (1) is 1: (0.05-100): (0.05-100).
Based on the technical scheme, further, the Au precursor in the step (1) is chloroauric acid, gold chloride, dipyridyl diphenylphosphine gold chloride, sodium tetrachloroaurate and hydrate thereof; the Ag precursor is silver nitrate, silver tetrafluoroborate, silver acetate, silver benzoate and hydrate thereof; the Cu precursor is copper nitrate, copper chloride, copper bromide and hydrates thereof.
Based on the above technical scheme, further, the phase transfer reagent in the step (2) is tetraoctylammonium bromide, tetrabutylammonium chloride and tetraethylammonium bromide, and the molar amount of the phase transfer reagent is 0.2-5 times of the total molar amount of the Au, Ag and Cu precursors.
Based on the technical scheme, further, the nitrogen-containing ligand in the step (3) is ethylenediamine, 4-tert-butylpyridine, dimethylaminopyridine, phenanthroline or imidazole; the sulfur-containing ligand is 1-adamantane thiol, p-fluorobenzene thiol, phenethyl thiol, 1-propanethiol, ethanedithiol or tert-butyl benzyl thiol; the alkynyl-containing ligand is 3-methylbutyne, tert-butyl acetylene or phenylacetylene; the molar weight of the ligand is 0.05-20 times of the total molar weight of the Au precursor, the Ag precursor and the Cu precursor.
Based on the technical scheme, further, the molar weight of the sodium borohydride in the step (4) is 0.5-20 times of the total molar weight of the Au precursor, the Ag precursor and the Cu precursor.
The invention also provides the AuAgCu three-component alloy nanocluster with controllable atomic number and size, which is prepared by the preparation method.
Based on the technical scheme, the size of the AuAgCu three-component alloy nano cluster is 0.3-3.0 nm.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention provides a method for preparing AuAgCu three-component alloy nanoclusters with controllable atomic number and size, which can realize the preparation of the AuAgCu three-component alloy nanoclusters in the same reaction system by using a simple one-step method. The method can be widely applied to the preparation of the alloy nanocluster containing the noble metal.
2. The preparation method is simple, convenient and feasible, is convenient to operate, and can directly prepare the heterogeneous AuAgCu alloy nanoclusters with controllable precise atomic number and size in the same reaction system by changing the precursor ratios of Au, Ag and Cu, the ligand types, the addition amount of the reducing agent, the reaction temperature and the reaction time.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the drawings to which the embodiments relate will be briefly described below.
Fig. 1 is an ultraviolet-visible absorption spectrum of the AuAgCu three-component alloy nanocluster product obtained in example 1.
Detailed Description
The present invention is described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto, and it is obvious that the examples in the following description are only some examples of the present invention, and it is obvious for those skilled in the art to obtain other similar examples without inventive exercise and falling into the scope of the present invention.
Example 1
Dissolving 34mg of chloroauric acid, 17mg of silver nitrate and 13mg of copper chloride in 3mL of water and 15mL of toluene, adding 274mg of tetraoctylammonium bromide, stirring at 45 ℃ for 40 minutes, then adding 85mg of 1-adamantanethiol, stirring at 25 ℃ for 2 hours, then dissolving 120mg of sodium borohydride in 5mL of water, slowly dropping the solution, and stirring at 15 ℃ for 1 hour; and (3) after the reaction is finished, spin-drying the product, washing the product for 3 times by using methanol, extracting by using dichloromethane, and spin-drying to obtain the AuAgCu alloy nanocluster product, wherein the specific reaction time can be determined according to the ultraviolet-visible absorption spectrum characterization result of the sample in the experimental process.
Example 2
Dissolving 41mg of chloroauric acid, 23mg of silver acetate and 39mg of copper bromide in 8mL of water and 25mL of toluene, adding 0.5g of tetrabutylammonium chloride, stirring at 35 ℃ for 60 minutes, then adding 45mg of ethylenediamine, stirring at 35 ℃ for 12 hours, then dissolving 120mg of sodium borohydride in 5mL of water, slowly adding dropwise the solution, and stirring at 5 ℃ for 5 hours; and (3) after the reaction is finished, spin-drying the product, washing the product for 3 times by using absolute ethyl alcohol, and extracting and spin-drying the product by using trichloromethane to obtain the AuAgCu alloy nano-cluster product.
Example 3
71mg of sodium tetrachloroaurate, 35mg of silver benzoate and 52mg of copper nitrate are dissolved in 3mL of water and 18mL of toluene, 0.36g of tetraethylammonium bromide is added, stirring is carried out for 15 minutes at 25 ℃, 85mg of dimethylaminopyridine is then added, stirring is carried out for 4 hours at 35 ℃, 85mg of sodium borohydride is then directly added into the solution, stirring is carried out for 5 hours at 25 ℃, the product is dried by spinning after the reaction is finished, the product is washed for 3 times by using methanol, and then dichloromethane is used for extraction and drying, so that the AuAgCu alloy nanocluster product is obtained.
Example 4
Dissolving 28mg of dipyridyldiphenylphosphine gold chloride, 26mg of silver tetrafluoroborate and 46mg of copper nitrate in 2mL of water and 18mL of toluene, adding 0.5g of tetrabutylammonium chloride, stirring for 10 minutes at 25 ℃, then adding 23mg of phenanthroline and 50mg of phenylacetylene, stirring for 6 hours at 30 ℃, then dissolving 75mg of sodium borohydride in 5mL of water, slowly dropping into the solution, stirring for 6 hours at 15 ℃, spin-drying the product after the reaction is finished, washing for 3 times by using deionized water and methanol respectively, and extracting and spin-drying by using dichloromethane to obtain the AuAgCu alloy nanocluster product.
Example 5
10mg of chloroauric acid, 15mg of silver acetate and 41mg of cupric chloride were dissolved in 30mL of toluene, 0.25g of tetraoctylammonium bromide was added, and the mixture was stirred at 40 ℃ for 180 minutes, followed by addition of 6mg of 4-t-butylpyridine, 15mg of 1-adamantanethiol and 8mg of t-butylacetylene, and stirring at 25 ℃ for 3 hours. Then 50mg of sodium borohydride was added directly to the above solution and stirred at 5 ℃ for 5 hours. And (3) after the reaction is finished, spin-drying the product, washing the product for 3 times by using absolute ethyl alcohol, and extracting and spin-drying the product by using trichloromethane to obtain the AuAgCu alloy nano-cluster product.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. A preparation method of an AuAgCu three-component alloy nano cluster with controllable atomic number and size is characterized by mainly comprising the following steps:
(1) dissolving an Au precursor, an Ag precursor and a Cu precursor in toluene or a mixed solution of water and toluene to obtain a reaction system 1;
(2) adding a phase transfer reagent into the reaction system 1, and stirring for 5-180 minutes at 3-85 ℃ to obtain a reaction system 2;
(3) adding one or more of a nitrogen-containing ligand, a sulfur-containing ligand and an alkynyl-containing ligand into the reaction system 2, and stirring for 0.1-24 hours at 5-70 ℃ to obtain a reaction system 3;
(4) adding sodium borohydride into the reaction system 3, and stirring and reacting for 0.1-144 hours at 5-90 ℃ to obtain a product;
(5) and (4) separating, spin-drying, washing and extracting the product obtained in the step (4) to obtain the AuAgCu three-component alloy nanocluster with controllable atom number and size.
2. The method according to claim 1, wherein the molar ratio of the Au precursor to the Ag precursor to the Cu precursor in step (1) is 1: (0.05-100): (0.05-100).
3. The preparation method according to claim 1, wherein the Au precursor in step (1) is chloroauric acid, gold chloride, dipyridyldiphenylphosphine gold chloride, sodium tetrachloroaurate, or a hydrate thereof; the Ag precursor is silver nitrate, silver tetrafluoroborate, silver acetate, silver benzoate and hydrates thereof; the Cu precursor is cupric nitrate, cupric chloride, cupric bromide and hydrate thereof.
4. The preparation method according to claim 1, wherein the phase transfer reagent in step (2) is tetraoctylammonium bromide, tetrabutylammonium chloride or tetraethylammonium bromide, and the molar amount of the phase transfer reagent is 0.2-5 times of the total molar amount of the Au, Ag and Cu precursors.
5. The method according to claim 1, wherein the nitrogen-containing ligand in step (3) is ethylenediamine, 4-t-butylpyridine, dimethylaminopyridine, phenanthroline, or imidazole; the sulfur-containing ligand is 1-adamantane thiol, p-fluorobenzene thiol, phenethyl thiol, 1-propanethiol, ethanedithiol or tert-butyl benzyl thiol; the alkynyl-containing ligand is 3-methylbutyne, tert-butyl acetylene or phenylacetylene; the molar weight of the ligand is 0.05-20 times of the total molar weight of the Au precursor, the Ag precursor and the Cu precursor.
6. The preparation method according to claim 1, wherein the molar amount of the sodium borohydride in the step (4) is 0.5 to 20 times of the total molar amount of the Au, Ag and Cu precursors.
7. The AuAgCu three-component alloy nanocluster prepared by the preparation method of any one of claims 1 to 6 and having controllable atomic number and size.
8. The AuAgCu three-component alloy nanocluster according to claim 7, wherein the AuAgCu three-component alloy nanocluster has a size of 0.3-3.0 nm.
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