CN114888300A - AuAgCu three-component alloy nano-cluster with controllable atomic number and size and preparation method thereof - Google Patents

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

A kind of AuAgCu three-component alloy nanoclusters with controllable number of atoms and size and preparation method thereof

technical field

The invention belongs to the technical field of metal alloy nano-clusters, in particular to an AuAgCu three-component alloy nano-cluster with controllable atomic number and size and a preparation method thereof.

Background technique

In recent years, the preparation of metal nanomaterials has attracted more and more attention. Metal nanoclusters usually refer to metal particles with a size of less than 3 nm and with precise metal atomic and ligand numbers, precise crystal structure, and generally a core-shell structure composed of metals and ligands. Among them, the core is dominated by metal bonds, while the ligands coordinate with the metal as the shell, and the physical and chemical properties of metal nanoclusters can be controlled by controlling factors such as size, morphology, composition, or functional groups. Metal nanoclusters have great potential for applications in catalysis, sensing, bioimaging, drug delivery, and cancer therapy. Therefore, it is of great significance to prepare metal nanoclusters with precise atomic numbers and rich in different surface functional groups.

Currently, a series of binary alloy nanoclusters have been synthesized. For example, the group of Zheng Nanfeng successfully synthesized Au ₂₄ Ag ₂₀ alloy nanoclusters using cationic ligands and obtained its crystal structure (J.Am.Chem.Soc., 2015, 137, 4324-4327). However, it is still a challenge to efficiently synthesize ternary alloy nanoclusters with different sizes and precise atomic numbers due to the cumbersome steps and complicated operations of many current metal nanocluster synthesis methods.

SUMMARY OF THE INVENTION

In view of this, the purpose of the present invention is to provide an AuAgCu three-component alloy nanocluster with controllable atomic number and size and a preparation method thereof, and a one-step method to synthesize AuAgCu three-component alloy with precise atomic number and controllable size Nanoclusters, the method is simple, feasible and easy to operate. By changing the ratio of Au, Ag, and Cu precursors, the type of ligand, the amount of reducing agent added, the reaction temperature and the reaction time, it is possible to directly prepare precise atoms in the same reaction system. Heterogeneous AuAgCu alloy nanoclusters with controllable number and size.

To achieve the above object, the present invention adopts the following technical solutions:

A preparation method of AuAgCu three-component alloy nanoclusters with controllable number of atoms and size, mainly comprising the following steps:

(1) Dissolving Au precursor, Ag precursor and Cu precursor in toluene or a mixed solution of water and toluene to obtain reaction system 1;

(2) adding a phase transfer reagent to reaction system 1, and stirring at 3-85° C. for 5-180 minutes to obtain reaction system 2;

(3) adding one or more of nitrogen-containing ligands, sulfur-containing ligands and alkynyl-containing ligands to reaction system 2, and stirring at 5 to 70° C. for 0.1 to 24 hours to obtain reaction system 3;

(4) adding sodium borohydride to reaction system 3, and stirring reaction at 5～90 ℃ for 0.1～144 hours to obtain the product;

(5) liquid separation, spin drying, washing and extraction of the product obtained in step (4) to obtain AuAgCu three-component alloy nanoclusters with controllable atomic number and size.

Based on the above technical solution, further, the molar ratio of the Au precursor, the Ag precursor, and the Cu precursor in step (1) is 1:(0.05-100):(0.05-100).

Based on the above technical solutions, further, the Au precursors described in step (1) are chloroauric acid, gold chloride, dipyridyldiphenylphosphine gold chloride, sodium tetrachloroaurate and its hydrate; the The Ag precursors are silver nitrate, silver tetrafluoroborate, silver acetate, silver benzoate and their hydrates; the Cu precursors are copper nitrate, copper chloride, copper bromide and their hydrates.

Based on the above technical solutions, further, the phase transfer reagents described in step (2) are tetraoctylammonium bromide, tetrabutylammonium chloride, and tetraethylammonium bromide, and the molar amount of the phase transfer reagents is Au , 0.2 to 5 times the total molar amount of Ag and Cu precursors.

Based on the above technical solution, further, the nitrogen-containing ligand described in step (3) is ethylenediamine, 4-tert-butylpyridine, dimethylaminopyridine, o-phenanthroline or imidazole; the sulfur-containing ligand is 1-adamantanethiol, p-fluorobenzenethiol, phenylethanethiol, 1-propanethiol, ethanedithiol or tert-butylbenzylthiol; the alkynyl-containing ligand is 3-methylbutyne , tert-butylacetylene or phenylacetylene; the molar amount of the ligand is 0.05-20 times the total molar amount of the Au, Ag and Cu precursors.

Based on the above technical solution, further, the molar amount of sodium borohydride in step (4) is 0.5 to 20 times the total molar amount of Au, Ag, and Cu precursors.

The present invention also provides AuAgCu three-component alloy nano-clusters with controllable atomic number and size prepared by the above preparation method.

Based on the above technical solutions, further, the size of the AuAgCu three-component alloy nano-clusters is 0.3-3.0 nm.

The beneficial effects that the present invention has with respect to the prior art are as follows:

1. The present invention provides a method for preparing AuAgCu three-component alloy nanoclusters with controllable number of atoms and size, which can realize the preparation of AuAgCu three-component alloy nanoclusters by a simple one-step method in the same reaction system. This method can be generally applied to the preparation of noble metal-containing alloy nanoclusters.

2. The preparation method of the present invention is simple, feasible, and easy to operate. By changing the ratio of Au, Ag, and Cu precursors, the type of ligand, the amount of reducing agent added, the reaction temperature and the reaction time, it is possible to directly prepare in the same reaction system. Heterogeneous AuAgCu alloy nanoclusters with controllable atomic number and size.

Description of drawings

In order to describe the embodiments of the present invention more clearly, the accompanying drawings related to the embodiments will be briefly introduced below.

FIG. 1 is an ultraviolet-visible absorption spectrum of the AuAgCu three-component alloy nanocluster product obtained in Example 1.

Detailed ways

The present invention will be described in detail below in conjunction with the examples, but the embodiments of the present invention are not limited thereto. Obviously, the examples in the following description are only part of the examples of the present invention. Under the premise of creative work, obtaining other similar embodiments falls within the protection scope of the present invention.

Example 1

34 mg of chloroauric acid, 17 mg of silver nitrate and 13 mg of copper chloride were dissolved in 3 mL of water and 15 mL of toluene, 274 mg of tetraoctyl ammonium bromide was added, stirred at 45°C for 40 minutes, followed by 85 mg of 1-adamantanethiol, Stir at 25 °C for 2 hours, then dissolve 120 mg of sodium borohydride in 5 mL of water, slowly add dropwise to the above solution, and stir for 1 hour at 15 °C; The AuAgCu alloy nano-cluster product is obtained by extraction with dichloromethane and spin-drying. The specific reaction time can be determined according to the characterization results of the UV-visible absorption spectrum of the sample during the experiment.

Example 2

Dissolve 41 mg of chloroauric acid, 23 mg of silver acetate and 39 mg of copper bromide in 8 mL of water and 25 mL of toluene, add 0.5 g of tetrabutylammonium chloride, stir at 35 ° C for 60 minutes, then add 45 mg of ethylenediamine, and at 35 Stir at ℃ for 12 hours, then dissolve 120 mg of sodium borohydride in 5 mL of water, slowly add it dropwise to the above solution, and stir at 5 ℃ for 5 hours; Use chloroform to extract and spin dry to obtain AuAgCu alloy nano-cluster products.

Example 3

Dissolve 71 mg of sodium tetrachloroaurate, 35 mg of silver benzoate and 52 mg of copper nitrate in 3 mL of water and 18 mL of toluene, add 0.36 g of tetraethylammonium bromide, stir at 25°C for 15 minutes, and then add 85 mg of dimethylaminopyridine , stirred at 35 ° C for 4 hours, then directly added 85 mg of sodium borohydride to the above solution, stirred at 25 ° C for 5 hours, after the reaction was completed, the product was spin-dried, washed with methanol 3 times, and then used dichloromethane Extraction and spin drying to obtain AuAgCu alloy nano-cluster products.

Example 4

28 mg of dipyridyldiphenylphosphine gold chloride, 26 mg of silver tetrafluoroborate, and 46 mg of copper nitrate were dissolved in 2 mL of water and 18 mL of toluene, 0.5 g of tetrabutylammonium chloride was added, and the mixture was stirred at 25°C for 10 minutes, followed by Add 23 mg o-phenanthroline and 50 mg phenylacetylene, stir at 30 ° C for 6 hours, then dissolve 75 mg of sodium borohydride in 5 mL of water, slowly add it dropwise to the above solution, and stir at 15 ° C for 6 hours. The product was spin-dried, washed three times with deionized water and methanol respectively, and then extracted with dichloromethane and spin-dried to obtain an AuAgCu alloy nano-cluster product.

Example 5

10 mg of chloroauric acid, 15 mg of silver acetate and 41 mg of copper chloride were dissolved in 30 mL of toluene, 0.25 g of tetraoctyl ammonium bromide was added, and stirred at 40°C for 180 minutes, followed by the addition of 6 mg of 4-tert-butylpyridine, 15 mg of 1 - Adamantanethiol, 8 mg of tert-butylacetylene, stirred at 25°C for 3 hours. Then 50 mg of sodium borohydride was directly added to the above solution and stirred at 5°C for 5 hours. After the reaction is completed, the product is spin-dried, washed three times with absolute ethanol, extracted with chloroform, and spin-dried to obtain an AuAgCu alloy nano-cluster product.

Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, but not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: The technical solutions described in the foregoing embodiments can still be modified, or some or all of the technical features thereof can be equivalently replaced; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the technical solutions of the embodiments of the present invention. scope.

Claims (8)

1. a preparation method of AuAgCu three-component alloy nano-clusters with controllable atomic number and size, is characterized in that, mainly comprises the following steps: (1) Dissolving Au precursor, Ag precursor and Cu precursor in toluene or a mixed solution of water and toluene to obtain reaction system 1; (2) adding a phase transfer reagent to reaction system 1, and stirring at 3-85° C. for 5-180 minutes to obtain reaction system 2; (3) adding one or more of nitrogen-containing ligands, sulfur-containing ligands and alkynyl-containing ligands to reaction system 2, and stirring at 5 to 70° C. for 0.1 to 24 hours to obtain reaction system 3; (4) adding sodium borohydride to reaction system 3, and stirring reaction at 5～90 ℃ for 0.1～144 hours to obtain the product; (5) liquid separation, spin drying, washing and extraction of the product obtained in step (4) to obtain AuAgCu three-component alloy nanoclusters with controllable atomic number and size. 2 . The preparation method according to claim 1 , wherein the molar ratio of the Au precursor, the Ag precursor and the Cu precursor described in the step (1) is 1: (0.05～100): (0.05～100 . 3 . ). 3. preparation method according to claim 1, is characterized in that, Au precursor described in step (1) is chloroauric acid, gold chloride, dipyridyldiphenylphosphine gold chloride, tetrachloroauric acid Sodium and its hydrate; the Ag precursors are silver nitrate, silver tetrafluoroborate, silver acetate, silver benzoate and their hydrates; the Cu precursors are copper nitrate, copper chloride, copper bromide and their hydrates thing. 4. preparation method according to claim 1, is characterized in that, described in step (2), the phase transfer reagent is tetraoctylammonium bromide, tetrabutylammonium chloride, tetraethylammonium bromide, described The molar amount of the phase transfer reagent is 0.2 to 5 times the total molar amount of the Au, Ag and Cu precursors. 5. preparation method according to claim 1, is characterized in that, nitrogen-containing ligand described in step (3) is ethylenediamine, 4-tert-butylpyridine, dimethylaminopyridine, o-phenanthroline or imidazole ; The sulfur-containing ligand is 1-adamantanethiol, p-fluorobenzenethiol, phenylethanethiol, 1-propanethiol, ethanedithiol or tert-butylbenzylthiol; the alkynyl-containing ligand The ligand is 3-methylbutyne, tert-butylacetylene or phenylacetylene; the molar amount of the ligand is 0.05-20 times the total molar amount of the Au, Ag and Cu precursors. 6 . The preparation method according to claim 1 , wherein the molar amount of sodium borohydride in step (4) is 0.5 to 20 times the total molar amount of Au, Ag, and Cu precursors. 7 . 7. AuAgCu three-component alloy nanoclusters with controllable atomic number and size prepared by the preparation method according to any one of claims 1-6. 8 . The AuAgCu three-component alloy nanocluster according to claim 7 , wherein the size of the AuAgCu three-component alloy nanocluster is 0.3-3.0 nm. 9 .

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