Preparation method of cubic pyramid porous silver micro-nano material

Abstract

The application relates to a preparation method of cubic pyramid porous silver micro-nano materials and belongs to the technical field of inorganic nano material preparation. The method comprises the following steps: (1) calcining a copper-based carrier, then reducing the copper-based carrier by hydrogen, and then soaking the reduced copper-based carrier in a stannous chloride ethanol solution to obtain a treated copper-based carrier; (2) dissolving silver salt in pure water to obtain a silver salt solution; then adding a chelating agent into the silver salt solution and stirring uniformly to obtain a precursor solution; and (3) placing the treated copper-based carrier into the precursor solution, stirring, cleaning, and naturally drying to obtain a copper-based carrier loaded cubic pyramid micro-nano porous silver. The preparation method of the cubic pyramid porous silver micro-nano material provided by the application realizes in-situ generation of nano porous silver in a silver complex reaction precursor solution by taking copper as a base carrier and stannous chloride as a sensitizing agent, and has the advantages of few steps, simple operation, low cost, good repeatability and suitability for large-scale industrial production.

Description

Technical Field

[0001] This invention relates to a method for preparing cubic pyramidal porous silver micro / nanomaterials, belonging to the field of inorganic nanomaterial preparation technology. Background Technology

[0002] Silver nanomaterials, due to their high thermal and electrical conductivity, antibacterial properties, and catalytic activity, have potential applications in microelectronics, biosensors, data storage, pharmaceutical antibacterial applications, and surface-enhanced Raman spectroscopy, and are considered a promising noble metal material. The performance of silver nanomaterials largely depends on their shape, size, and composition; therefore, synthesizing silver nanomaterials with different structures is of great significance for the research of nanosilver. Nanoporous silver, due to its porosity, possesses characteristics such as large specific surface area, low relative density, low thermal conductivity, and good energy absorption performance, and has been widely used in aerospace, electronic communications, petrochemicals, and transportation. Currently, the main methods for preparing nanoporous silver include electrochemical deposition, polymer synthesis, and dealloying.

[0003] Chinese patent document CN115971506A discloses a chemical self-assembly method for large-size porous silver. This method uses silver nitrate solution as a precursor and prepares porous silver micro / nanostructures resembling stacked silver needles, silver coral, silver snowflakes, and silver spheres by controlling the reducing agent, pH value, and temperature. However, the porous silver prepared by this patent method is a physically stacked structure, which suffers from poor pore channel adjustability and uniformity. Chinese patent document CN115229200A discloses a method for preparing cubic porous silver micromaterials. This method grows cubic cuprous oxide nanomaterials on the surface of a copper sheet via electrochemical oxidation, and then uses the prepared cuprous oxide nanomaterials as templates for displacement in a silver nitrate solution to obtain cubic porous silver micromaterials on the copper sheet surface. However, the porous silver prepared by this patent method is mostly a copper-silver alloy structure, making it difficult to obtain elemental silver micro / nanomaterials. Therefore, there is an urgent need to develop a new method for preparing porous silver micro / nanomaterials that can overcome the problems of existing technologies. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides a method for preparing cubic pyramidal porous silver micro / nanomaterials.

[0005] The technical solution of the present invention is as follows:

[0006] A method for preparing cubic pyramidal porous silver micro / nanomaterials includes the following steps:

[0007] (1) Treatment of copper-based support: Calcine the copper-based support at 700-1100℃ for 5-7h, cool it to room temperature, then reduce it with hydrogen at 100-500℃ for 1.5-2.5h, cool it to room temperature, soak the reduced copper-based support in ethanol solution of stannous chloride for 25-35min, take it out and dry it naturally to obtain the treated copper-based support;

[0008] (2) Preparation of precursor solution: Dissolve silver salt in pure water to obtain a silver salt solution with a concentration of 4-60 mmol / L; then add chelating agent to the silver salt solution and stir evenly to obtain the precursor solution;

[0009] (3) Preparation of porous silver: The treated copper-based support is placed in the precursor solution and stirred for 1.5 to 2.5 min. After being taken out, it is washed and dried naturally to obtain cubic pyramidal micro-nano porous silver loaded on the copper-based support.

[0010] According to a preferred embodiment of the present invention, in step (1), the copper-based carrier is copper foil, copper mesh, and copper wire.

[0011] According to a preferred embodiment of the present invention, in step (1), the calcination is carried out in a muffle furnace at a calcination temperature of 800–1000°C.

[0012] According to a preferred embodiment of the present invention, in step (1), the reduction is carried out in a tube furnace at a calcination temperature of 100–500°C.

[0013] According to a preferred embodiment of the present invention, in step (1), the concentration of the ethanol solution of stannous chloride is 0.05 to 0.3 mol / L.

[0014] More preferably, the concentration of the stannous chloride ethanol solution is 0.1–0.3 mol / L.

[0015] According to a preferred embodiment of the present invention, in step (2), the silver salt is silver nitrate, silver acetate, silver perchlorate, or silver phosphate.

[0016] According to a preferred embodiment of the present invention, in step (2), the concentration of the silver salt is 10 to 30 mmol / L.

[0017] According to a preferred embodiment of the present invention, in step (2), the chelating agent is triethanolamine or ethylenediamine.

[0018] According to a preferred embodiment of the present invention, in step (2), the volume ratio of the chelating agent to the silver salt solution is 1:20.

[0019] According to a preferred embodiment of the present invention, in step (2), the cleaning is performed by rinsing with deionized water 3 to 5 times.

[0020] The present invention also provides cubic pyramidal micro / nano porous silver prepared according to the above preparation method.

[0021] The technical features and beneficial effects of this invention are as follows:

[0022] 1. This invention provides a method for in-situ growth of cubic pyramidal porous silver micro / nanomaterials in solution. Specifically, copper is used as a substrate, stannous chloride is used as a sensitizer, and a silver complex is grown in situ. Uniform cubic pyramidal porous silver micro / nanomaterials are directly prepared in the precursor solution of the silver complex reaction. This method has the advantages of fewer steps, simple operation, low cost, and good reproducibility, making it suitable for large-scale industrial production.

[0023] 2. The nanoporous silver prepared by this invention has a cubic pyramidal structure, which has a larger specific surface area and is evenly distributed compared to other silver nanostructures, exhibiting good uniformity. Attached Figure Description

[0024] Figure 1 This is a scanning electron microscope image of the cubic pyramidal nanoporous silver prepared in Example 1 of this invention.

[0025] Figure 2 This is the X-ray diffraction pattern of the cubic pyramidal nanoporous silver prepared in Example 1 of this invention. Detailed Implementation

[0026] The present invention will be further described below with reference to specific embodiments and accompanying drawings, but these are not intended to limit the scope of protection of the present invention.

[0027] All raw materials and equipment used in the examples are conventional and can be purchased commercially.

[0028] Example 1

[0029] A method for preparing cubic pyramidal porous silver micro / nanomaterials includes the following steps:

[0030] (1) Treatment of copper-based support: The copper-based support was placed in a muffle furnace and calcined at 900℃ for 6 hours. After cooling to room temperature, it was placed in a tube furnace and reduced with hydrogen at 250℃ for 2 hours. After cooling to room temperature, the reduced copper-based support was soaked in 50 mL of ethanol solution with a concentration of 0.2 mol / L stannous chloride for 30 minutes. After being taken out and dried naturally, the treated copper-based support was obtained.

[0031] (2) Preparation of precursor solution: Dissolve 1 mmol silver nitrate in 50 mL of pure water to obtain a silver nitrate solution with a concentration of 20 mmol / L; then add 2.5 mL of triethanolamine to the silver nitrate solution and stir evenly to obtain the precursor solution;

[0032] (3) Preparation of micro-nano porous silver: The treated copper-based carrier was placed in the precursor solution and stirred for 2 min. After being taken out, it was washed 4 times with deionized water and dried naturally to obtain cubic cone-shaped micro-nano porous silver.

[0033] The cubic pyramidal porous silver scanning electron microscope image prepared in this embodiment is shown below. Figure 1 As shown, the X-ray diffraction pattern is as follows: Figure 2 As shown. By Figure 1 and Figure 2 It can be seen that the prepared material is a cubic pyramidal porous micro / nano material rich in pore structure. Its X-ray diffraction pattern shows obvious Ag(111) plane diffraction characteristic peak at the 38.1 degree position, which indicates that a cubic pyramidal porous silver material was successfully prepared in this embodiment.

[0034] Example 2

[0035] A method for preparing a cubic pyramidal porous silver micro / nanomaterial, the steps are the same as in Example 1, except that the calcination temperature in step (1) is 700℃.

[0036] Example 3

[0037] A method for preparing a cubic pyramidal porous silver micro / nanomaterial, the steps are the same as in Example 1, except that the calcination temperature in step (1) is 800℃.

[0038] Example 4

[0039] A method for preparing a cubic pyramidal porous silver micro / nanomaterial, the steps are the same as in Example 1, except that the calcination temperature in step (1) is 1000℃.

[0040] Example 5

[0041] A method for preparing a cubic pyramidal porous silver micro / nanomaterial, the steps are the same as in Example 1, except that the calcination temperature in step (1) is 1100℃.

[0042] Example 6

[0043] A method for preparing a cubic pyramidal porous silver micro / nanomaterial, the steps are the same as in Example 1, except that the reduction temperature in step (1) is 100℃.

[0044] Example 7

[0045] A method for preparing a cubic pyramidal porous silver micro / nanomaterial, the steps are the same as in Example 1, except that the reduction temperature in step (1) is 400℃.

[0046] Example 8

[0047] A method for preparing cubic pyramidal porous silver micro / nanomaterials, the steps are the same as in Example 1, except that the reduction temperature in step (1) is 500℃.

[0048] Example 9

[0049] A method for preparing a cubic pyramidal porous silver micro / nanomaterial, the steps are the same as in Example 1, except that the concentration of the ethanol solution of stannous chloride in step (1) is 0.05 mol / L.

[0050] Example 10

[0051] A method for preparing a cubic pyramidal porous silver micro / nanomaterial, the steps are the same as in Example 1, except that the concentration of the ethanol solution of stannous chloride in step (1) is 0.1 mol / L.

[0052] Example 11

[0053] A method for preparing a cubic pyramidal porous silver micro / nanomaterial, the steps are the same as in Example 1, except that the concentration of the ethanol solution of stannous chloride in step (1) is 0.3 mol / L.

[0054] Example 12

[0055] A method for preparing a cubic pyramidal porous silver micro / nanomaterial, the steps are the same as in Example 1, except that the concentration of silver nitrate solution in step (1) is 4 mol / L.

[0056] Example 13

[0057] A method for preparing a cubic pyramidal porous silver micro / nanomaterial, the steps are the same as in Example 1, except that the concentration of silver nitrate solution in step (1) is 10 mol / L.

[0058] Example 14

[0059] A method for preparing a cubic pyramidal porous silver micro / nanomaterial, the steps are the same as in Example 1, except that the concentration of silver nitrate solution in step (1) is 30 mol / L.

[0060] Example 15

[0061] A method for preparing a cubic pyramidal porous silver micro / nanomaterial, the steps are the same as in Example 1, except that the concentration of silver nitrate solution in step (1) is 60 mol / L.

[0062] Example 16

[0063] A method for preparing a cubic pyramidal porous silver micro / nanomaterial, the steps are the same as in Example 1, except that silver acetate is used instead of silver nitrate in step (2).

[0064] Example 17

[0065] A method for preparing a cubic pyramidal porous silver micro / nanomaterial, the steps are the same as in Example 1, except that silver perchlorate is used instead of silver nitrate in step (2).

[0066] Example 18

[0067] A method for preparing a cubic pyramidal porous silver micro / nanomaterial, the steps are the same as in Example 1, except that silver phosphate is used instead of silver nitrate in step (2).

[0068] Example 19

[0069] A method for preparing a cubic pyramidal porous silver micro / nanomaterial, the steps are the same as in Example 1, except that in step (2), ethylenediamine is used instead of triethanolamine.

Claims

1. A method for preparing cubic pyramidal porous silver micro / nanomaterials, characterized in that, The steps include the following: (1) Treatment of copper-based support: Calcine the copper-based support at 800~1000℃ for 5~7h, cool it to room temperature, then reduce it with hydrogen at 100~500℃ for 1.5~2.5h, cool it to room temperature, soak the reduced copper-based support in ethanol solution of stannous chloride for 25~35min, take it out and dry it naturally to obtain the treated copper-based support; The calcination is carried out in a muffle furnace; the hydrogen reduction is carried out in a tube furnace; and the concentration of the stannous chloride ethanol solution is 0.05~0.3 mol / L. (2) Preparation of precursor solution: Dissolve silver salt in pure water to obtain a silver salt solution with a concentration of 4~60 mmol / L; then add chelating agent to the silver salt solution and stir evenly to obtain the precursor solution; The chelating agent is triethanolamine or ethylenediamine; the volume ratio of the chelating agent to the silver salt solution is 1:

20. (3) Preparation of porous silver: The treated copper-based support is placed in the precursor solution and stirred for 1.5~2.5 min. After being taken out, it is washed and dried naturally to obtain cubic pyramidal micro-nano porous silver loaded on the copper-based support.

2. The method for preparing cubic pyramidal porous silver micro / nanomaterials as described in claim 1, characterized in that, In step (1), the copper-based carrier is copper foil, copper mesh, and copper wire.

3. The method for preparing cubic pyramidal porous silver micro / nanomaterials as described in claim 1, characterized in that, In step (1), the concentration of the ethanol solution of stannous chloride is 0.1~0.3 mol / L.

4. The method for preparing cubic pyramidal porous silver micro / nanomaterials as described in claim 1, characterized in that, In step (2), the silver salt is silver nitrate, silver acetate, silver perchlorate or silver phosphate.

5. The method for preparing cubic pyramidal porous silver micro / nanomaterials as described in claim 1, characterized in that, In step (2), the concentration of the silver salt is 10~30 mmol / L.

6. The cubic pyramidal porous silver micro / nanoporous material prepared by the method for preparing cubic pyramidal porous silver micro / nanoporous material according to any one of claims 1 to 5.

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