阅读说明：本技术 一种半核壳Au/Cu2-xS异质纳米材料及其制备方法 (Half-core-shell Au/Cu2-xS heterogeneous nano material and preparation method thereof ) 是由 马良 陈相柏 于 2019-08-14 设计创作，主要内容包括：本发明涉及一种半核壳Au/Cu_(2-x)S异质纳米材料的制备方法,包括如下步骤：S1.在十六烷基三甲基溴化氨体系下制备纳米金胶体溶液,纳米金的粒径为18-22nm；S2.采用水相合成法以纳米金为生长底衬,以硫代乙酰胺和乙酸铜为前驱体,以抗坏血酸为还原剂,十六烷基三甲基溴化氨为辅助生长剂,在六亚甲基四胺存在的条件下真空下反应得到半核壳Au/Cu_(2-x)S异质纳米材料水溶液；S3.分离、清洗干燥得到半核壳Au/Cu_(2-x)S异质纳米材料。本方法简洁可控,制备出的半核壳Au/Cu_(2-x)S异质纳米材料的产率大于97％,并且具有优异的双等离激元增强的光催化和多相类芬顿催化活性。(The invention relates to a half core-shell Au/Cu 2‑x The preparation method of the S heterogeneous nano material comprises the following steps: s1, preparing a nano gold colloidal solution in a hexadecyl trimethyl ammonium bromide system, wherein the particle size of nano gold is 18-22 nm;s2, reacting nano-gold serving as a growth substrate, thioacetamide and copper acetate serving as precursors, ascorbic acid serving as a reducing agent and cetyl trimethyl ammonium bromide serving as an auxiliary growth agent in the presence of hexamethylenetetramine in vacuum by adopting a water phase synthesis method to obtain semi-core-shell Au/Cu 2‑x S heterogeneous nano material aqueous solution; s3, separating, cleaning and drying to obtain semi-core-shell Au/Cu 2‑x S heterogeneous nano material. The method is simple and controllable, and the prepared half core-shell Au/Cu 2‑x The yield of the S heterogeneous nano material is more than 97%, and the S heterogeneous nano material has excellent double-plasmon enhanced photocatalysis and multiphase Fenton-like catalytic activity.)

1. Half-core-shell Au/Cu_2-xThe preparation method of the S heterogeneous nano material is characterized by comprising the following steps:

s1, preparing a nano gold colloidal solution in a hexadecyl trimethyl ammonium bromide system, wherein the particle size of nano gold is 18-22 nm;

s2, adopting a water phase synthesis method to obtain the sodiumThe mijin is taken as a growth substrate, thioacetamide and cupric acetate are taken as precursors, ascorbic acid is taken as a reducing agent, cetyl trimethyl ammonium bromide is taken as an auxiliary growth agent, and the reaction is carried out in vacuum in the presence of hexamethylenetetramine to obtain the semi-core-shell Au/Cu_2-xS is heterogeneous nano material water solution, the concentrations of the nano gold, thioacetamide, copper acetate, ascorbic acid, hexamethylenetetramine and hexadecyl trimethyl ammonium bromide in a reaction system are 26.88-32.86nM, 0.67-1mM, 0.25-0.47mM, 8.36-15.53mM and 8.36-15.53mM respectively, the reaction temperature is 86-94 ℃, and the reaction time is 2.8-3.2 h;

s3, enabling the half core shell to be Au/Cu_2-xCentrifuging the S heterogeneous nano material aqueous solution to obtain a solid product, and cleaning and drying the solid product to obtain the semi-core-shell Au/Cu_2-xS heterogeneous nano material.

2. Half core-shell Au/Cu according to claim 1_2-xThe preparation method of the S heterogeneous nano material is characterized in that the step S1 comprises the following steps:

s1.1, adding a chloroauric acid solution, hexadecyl trimethyl ammonium bromide and a sodium borohydride solution into deionized water to react to obtain a nano gold seed solution;

s1.2, mixing a chloroauric acid solution, an ascorbic acid solution and a hexadecyl trimethyl ammonium bromide solution to obtain a first mixed solution, adding the nano gold seed solution obtained in the step S1.1 into the first mixed solution, adjusting the pH value to 11.3-11.7, and reacting to obtain the nano gold colloidal solution.

3. Half core-shell Au/Cu according to claim 2_2-xThe preparation method of the S heterogeneous nano material is characterized in that the sodium borohydride solution is a sodium borohydride ice-water mixture.

4. Half core-shell Au/Cu according to claim 3_2-xThe preparation method of the S heterogeneous nano material is characterized in that the volume fractions of the deionized water, the chloroauric acid solution, the hexadecyl trimethyl ammonium bromide and the sodium borohydride solution in the step S1.1The concentrations of the chloroauric acid solution, the hexadecyl trimethyl ammonium bromide and the sodium borohydride solution are respectively 0.048-0.052M, 0.17-0.23M and 0.009-0.011M when the concentrations are respectively 5mL, 500 μ L, 4.5mL and 600 μ L, the reaction time is 2-2.5h, and the stirring is carried out at 1000 revolutions per minute during the reaction process.

5. Half core-shell Au/Cu according to claim 4_2-xThe preparation method of the S heterogeneous nano material is characterized in that when the volumes of the nano gold seed solution, the chloroauric acid solution, the ascorbic acid solution and the hexadecyl trimethyl ammonium bromide solution in the step S1.2 are 60 muL, 18mL, 10.5mL and 90mL respectively, the concentrations of the chloroauric acid solution, the ascorbic acid solution and the hexadecyl trimethyl ammonium bromide are 4.5-5.5mM, 8-16mM and 0.17-0.23M respectively, the reaction time is 1-2h, after the reaction is finished, a reaction product is centrifuged at 10000rpm/min for 15min, and the precipitate is redispersed in deionized water.

6. A half core-shell Au/Cu according to any one of claims 1 to 5_2-xThe preparation method of the S heterogeneous nano material is characterized in that the specific step of the step S3 is to mix the half core-shell Au/Cu_2-xCooling the S heterogeneous nano material aqueous solution to normal temperature, centrifuging at 8000-10000rpm for 5 minutes to obtain a solid product, alternately cleaning the solid product with deionized water and ethanol, and placing the solid product in a forced air drying oven for 10-12 hours at 60-70 ℃ to obtain the semi-core-shell Au/Cu_2-xS heterogeneous nano material.

7. A half core-shell Au/Cu according to any one of claims 1 to 5_2-xThe preparation method of the S heterogeneous nano material is characterized in that the step S2 specifically comprises the following steps: taking 5mL of the nanogold colloidal solution prepared in the step S1, adjusting the concentration to 45-55nM, adding 1mL of ascorbic acid solution, 1mL of hexamethyltetramine solution, 1mL of hexadecyltrimethylammonium bromide solution, 70 mu L of thioacetamide solution and 300 mu L of cupric acetate solution to obtain a second mixed solution, transferring the second mixed solution into a reaction container for packaging, placing the reaction container into a vacuum drying oven, vacuumizing, and setting the temperature to be 86-94 ℃ for 2-reactionThe concentrations of the thioacetamide solution, the copper acetate solution, the ascorbic acid solution, the hexamethylenetetramine solution and the cetyltrimethylammonium bromide solution are 80-120mM, 7-13mM, 70-130mM and 170-230mM, respectively, for 8-3.2 hours.

8. Half-core-shell Au/Cu_2-xS heterogeneous nanomaterial, characterized in that it is prepared by the preparation method according to any one of claims 1 to 7.

Technical Field

The invention relates to the technical field of preparation of inorganic nano materials, in particular to half core-shell Au/Cu_2-xS heterogeneous nano material and a preparation method thereof.

Background

The metal-semiconductor heterogeneous nano material based on the plasmon shows great application potential in the field of photocatalytic solar energy conversion due to excellent photon absorption and photoelectric conversion characteristics generated by the synergistic effect of the plasmon and the semiconductor. The copper chalcogenide semiconductor is a photocatalyst with great development potential and is widely applied to the treatment of photocatalytic pollutants, and meanwhile, the copper chalcogenide and the gold nanocrystal are good Fenton-like catalysts, so that the catalytic efficiency of the single-component copper chalcogenide and gold nanocrystal Fenton-like reaction prepared in experiments at present is low, and the practical application of the single-component copper chalcogenide and gold nanocrystal is limited.

Disclosure of Invention

The invention provides a composite material containing Au and Cu for solving the technical problems_2-xS two plasmons enhance multiphase Fenton-like and photocatalytic reaction activity of half core-shell Au/Cu_2-xS heterogeneous nano material and a preparation method thereof.

The technical scheme for solving the technical problems is as follows: half-core-shell Au/Cu_2-xThe preparation method of the S heterogeneous nano material comprises the following steps:

s1, preparing a nano gold colloidal solution in a hexadecyl trimethyl ammonium bromide system, wherein the particle size of nano gold is 18-22 nm;

s2, reacting nano-gold serving as a growth substrate, thioacetamide and copper acetate serving as precursors, ascorbic acid serving as a reducing agent and cetyl trimethyl ammonium bromide serving as an auxiliary growth agent in the presence of hexamethylenetetramine in vacuum by adopting a water phase synthesis method to obtain semi-core-shell Au/Cu_2-xS heterogeneous nano material water solution, wherein the concentrations of the nano gold, the thioacetamide, the copper acetate, the ascorbic acid, the hexamethylenetetramine and the hexadecyl trimethyl ammonium bromide in a reaction system are respectively 26.88-32.86nM0.67-1mM, 0.25-0.47mM, 8.36-15.53mM, reaction temperature of 86-94 ℃ and reaction time of 2.8-3.2 h;

s3, enabling the half core shell to be Au/Cu_2-xCentrifuging the S heterogeneous nano material aqueous solution to obtain a solid product, and cleaning and drying the solid product to obtain the semi-core-shell Au/Cu_2-xS heterogeneous nano material.

The principle of the invention is as follows: under the action of ascorbic acid and hexadecyl trimethyl ammonium bromide, copper ions in copper acetate are complexed on the surface of the nano gold ball and react with thioacetamide to generate Cu_2-xS nanoshell, Cu produced_2-xS grows on the surface of the nanogold under the action of a reducing agent and an auxiliary growth agent to obtain semi-core-shell Au/Cu_2-xS heterogeneous nano material, ascorbic acid can be used as reducing agent, and can be complexed with hexadecyl trimethyl ammonium bromide to assist Cu_2-xAnd (4) growing S.

Drawings

FIG. 1 shows a half core-shell Au/Cu prepared in example 2 of the present invention_2-xS, a transmission electron microscope photo of the heterogeneous nano material;

FIG. 2 shows the results of the experiment in test example 1 of the present invention, in which FIG. 2a shows the results of the experiment using gold nanoparticles and Cu_2-xS, half core-shell Au/Cu_2-xS heterogeneous nano material and core-shell Au/Cu_2-xA catalytic decomposition rate diagram of the S heterogeneous nano material on methylene blue molecules under the conditions of hydrogen peroxide and no light; FIG. 2b shows half core-shell Au/Cu_2-xS, the catalytic degradation rate of the heterogeneous nano material to methylene blue molecules under the irradiation of monochromatic light with different wavelengths;

FIG. 3 shows gold nanoparticles and Cu in test example 2 of the present invention_2-xS, half core-shell Au/Cu_2-xS heterogeneous nano material and core-shell Au/Cu_2-xThe S heterogeneous nano material has photocatalytic degradation rate under the irradiation of light without the assistance of hydrogen peroxide.

Detailed Description

The principles and features of this invention are described in connection with the drawings and the detailed description of the invention, which are set forth below as examples to illustrate the invention and not to limit the scope of the invention.

All the solutions below are aqueous solutions unless otherwise specified.