A preparation method of ITO nanowire composite material

Abstract

The present invention discloses a method for preparing an ITO nanowire composite material, which belongs to the field of nanomaterial preparation technology. Using a secondary anodic aluminum oxide film as a template, an In9.45Sn alloy is pressed into the secondary anodic aluminum oxide film template by a physical hydraulic method at 5-20°C above its melting point. After dissolving and removing the aluminum oxide template, In9.45Sn nanowires are obtained. By adding a certain amount of soluble organic matter, In9.45Sn nanowires, and metal ion salts to an aqueous solution and reacting them under 120-200°C hydrothermal conditions for 2h, an ITO nanowire / metal oxide composite material is obtained. The morphology of the ITO nanowires prepared by this method is easy to control, which reduces the difficulty of preparing ITO nanowires and their composite materials.

Description

Technical field:

[0001] The present invention relates to a method for preparing nanowires of metal oxide (ITO) and its composite, and in particular to a nanomaterial preparation technology. Background technology:

[0002] In recent years, one-dimensional nanomaterials have rapidly developed due to their remarkable structural and functional properties, becoming an essential component of the field of functional nanodevices. The one-dimensional morphology can easily enhance the unique properties of metal oxide nanostructures, making them suitable for a wide range of applications, including gas sensors, electrochromic devices, light-emitting diodes, field emitters, supercapacitors, nanoelectronics, and nanogenerators. Therefore, finding simple and efficient methods to prepare one-dimensional nanostructured materials and fully realize their potential is an urgent challenge.

[0003] Various physical and chemical deposition techniques and growth mechanisms can be used to control the morphology of one-dimensional metal oxide nanostructures, so that they have uniform size, perfect crystal structure, defects and uniform stoichiometry. Its main synthesis methods include liquid phase method, electrospinning method, template method, etc. The electrospinning method is a typical method for preparing nanostructures. In the literature Electrospun carbon nanofiber-assisted patterning of metal oxide nanostructures (Islam M., Dolle C., Sadaf A., et al. Electrospun carbon nanofiber-assisted patterning of metal oxide nanostructures [J]. Microsystems & nanoengineering, 2022, 8 (1): 1-14.), AuCl3 and PANI were mixed in DMF solvent and AuCl3 / PAN nanofibers were obtained by electrospinning. Then, the electrospun nanofibers were carbonized at 900 ° C for 1 h under a constant argon flow to obtain AuNPs / C nanofibers. These AuNPs / C nanofibers were used as catalyst templates in a vapor-phase transport growth process, using a mixture of graphite powder and metal oxide powders as the source material and the AuNPs / C nanofibers as the growth substrate. This vapor-phase transport growth process resulted in the growth of metal oxide nanostructures on the nanofiber templates, producing nanowires. This example demonstrates the high production costs associated with expensive equipment and the resulting complex nanowires, resulting in a chaotically arranged structure.

[0004] The template method is a typical method for preparing nanostructures. In the patent "An Anodic Aluminum Oxide Template 'Melting-Injection-Decomposition'" (CN 105752938), a purely physical heating method is used to dissolve a metal nitrate into a fluid. The strong capillary action between the fluid and the nanoscale pores of the anodic aluminum oxide template then forces the fluid into the pores. As the temperature rises, the metal nitrate within the pores decomposes and, due to the template's pore-confining effect, forms a one-dimensional metal oxide nanowire array. This example demonstrates that common problems with the template method include a complex preparation process, a limited range of prepared materials, poor versatility, and difficulty in generalization.

[0005] The hydrothermal method is a typical method for preparing nanostructures based on liquid phase. In the literature "A Co3O4 / CuO composite nanowire array as a low-cost and efficient bifunctional electrocatalyst for water splitting" (Yang F, Guo Z, Zhang B, et al. A Co3O4 / CuO composite nanowire array as low-cost and efficient bifunctional electrocatalyst for water splitting [J]. Applied Physics A, 2021, 127 (5): 1-11.), Co(NO3)2·6H2O (0.25 mmol), Cu(NO3)2·H2O (0.75 mmol), Co(NH2)2 (1.5 mmol), ethylene glycol (4 ml) and deionized water (44 ml) were mixed and stirred, and the mixed solution was loaded on a nickel foam substrate and transferred to a 25 ml substrate autoclave and kept at 120 ° C for 6 hours. When the autoclave temperature dropped to room temperature, the nickel foam was removed and rinsed with distilled water, then dried at 60°C and annealed at 350°C for 2 hours (at a heating rate of 2°C / min) to produce nanowires. This example demonstrates the ability of the hydrothermal method to complete product formation and crystallization in a single step. This method is simple, allows for controlled product ratios to produce single-phase materials, is relatively inexpensive, and readily yields well-oriented, perfect crystals.

[0006] The hydrothermal method for preparing metal oxide nanomaterials avoids the potential for hard agglomeration of particles, and allows for control of the nanoparticles' crystal structure, morphology, and purity by adjusting reaction conditions. However, this method is highly dependent on production equipment, and in-depth research into factors influencing nucleation and crystal growth processes is lacking, resulting in no satisfactory conclusions. Therefore, finding a universal, controllable method for preparing metal oxide and composite nanomaterials remains a significant challenge. Summary of the invention:

[0007] In order to solve the shortcomings of the prior art, the present invention provides a method for preparing an ITO nanowire composite material. 9.45 On the basis of Sn nanowires, a certain amount of soluble organic matter, In 9.45 Sn nanowires and metal ions were hydrothermally reacted at 120-200°C for 2 hours to obtain an ITO nanowire / metal oxide composite. This method facilitates the coating process and product collection, broadening the approach to morphology preservation during the preparation of ITO nanowire / metal oxide composites and reducing the difficulty of preparation.

[0008] The technical solutions provided by the present invention are as follows:

[0009] Using the secondary anodic aluminum film as a template, the physical hydraulic method was used to 9.45 Sn is pressed into the secondary anodic aluminum oxide film template at a temperature 5-20°C above its melting point; after cooling, the secondary anodic aluminum oxide film template is placed in a (5-30) wt.% NaOH solution or an aqueous solution of (3-10) wt.% phosphoric acid and (1-3) wt.% chromic acid to dissolve and remove the template, and then ultrasonically cleaned and dried in an oven to obtain In. 9.45 Sn nanowires;

[0010] The prepared In 9.45 Sn nanowires, (1-10) wt.% soluble organic matter, and (1-5) wt.% metal ion salt are added to an aqueous solution and reacted under hydrothermal conditions of 120-200° C. for 2 hours to obtain an ITO nanowire / metal oxide composite material.

[0011] The diameter of the secondary anodic aluminum oxide film template is 10-500 nm, and the length is 1-500 μm.

[0012] The soluble organic matter is one or more of hexadecyltrimethylammonium bromide, methacryloxysilane, mercaptopropyltrimethoxysilane, N-methylpyrrolidone, ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, tetrasodium ethylenediaminetetraacetate, acrylonitrile, polyethylene glycol-200, polyethylene glycol-400, or polyvinylpyrrolidone.

[0013] The metal ion salt is one of nickel chloride, nickel acetate, nickel nitrate, nickel sulfate, cobalt chloride, cobalt acetate, cobalt nitrate, cobalt sulfate, ferric chloride, ferric acetate, ferric nitrate, ferric sulfate, copper sulfate, copper chloride, silver nitrate, ruthenium chloride, and chloroplatinic acid.

[0014] The metal oxide is one of nickel oxide, cobalt oxide, iron oxide, copper oxide, silver oxide, ruthenium oxide and platinum oxide. Specific implementation method:

[0015] Implementation Case 1:

[0016] A 5cm square aluminum sheet (purity greater than or equal to 99.9%, thickness 0.2mm) was machined to remove the surface oxide layer. The electrolyte was prepared from oxalic acid and deionized water, with an oxalic acid content of 0.1M. The treated aluminum sheet was placed in the reaction apparatus, with an area of 12.56cm exposed to the electrolyte. 2 The electrolyte temperature was fixed at 5°C in a refrigerator, and a carbon sheet was used as the cathode. Anodization was performed at an anode voltage of 20 V for 0.05 h to obtain a nanotube array membrane with an average pore size of 10 nm and a length of 1 μm.

[0017] Preparation of ITO / NiO nanowire arrays: The specific steps are as follows: Place the previously prepared alumina nanotube array film face up in a vacuum hydraulic device, and then place the melted In 9.45 Sn is pressed into a sheet and placed on top of the array membrane. The vacuum pump and heating device are turned on, and the device temperature is raised to 155°C, slightly higher than the melting point of the alloy. It is kept for 10 minutes, and the alloy melts and spreads on the surface of the array membrane. Then, a liquid pressure of about 40 MPa is applied to inject the alloy into the nanotube array membrane. After cooling to room temperature, the remaining In is peeled off. 9.45 Sn sheet, and then ultrasonically clean the alumina nanotube array membrane.

[0018] The membrane was placed in a 5 wt.% NaOH aqueous solution for template etching for 72 h, ultrasonically cleaned and dried to obtain In 9.45 Sn nanowire arrays.

[0019] In 9.45 Sn nanowire arrays, 1 wt.% nickel chloride, and 1 wt.% hexadecyltrimethylammonium bromide aqueous solution were hydrothermally reacted at 120° C. for 2 h, and the product was collected by centrifugation and dried to obtain an ITO / NiO composite material.

[0020] Implementation Case 2:

[0021] A 5cm square aluminum sheet (purity greater than or equal to 99.9%, thickness 0.2mm) was machined to remove the surface oxide layer. The electrolyte was prepared from oxalic acid and deionized water, with an oxalic acid content of 0.2M. The treated aluminum sheet was placed in the reaction apparatus, with an area of 12.56cm exposed to the electrolyte. 2 The electrolyte temperature was fixed at 5°C in a refrigerator, and a carbon sheet was used as the cathode. Anodization was performed at an anode voltage of 40 V for 0.1 h to obtain a nanotube array membrane with an average pore size of 40 nm and a length of 1 μm.

[0022] Preparation of ITO / NiO nanowire arrays: The specific steps are as follows: Place the previously prepared aluminum oxide nanotube array film face up in a vacuum hydraulic device, and then place the metal In 9.45 A Sn alloy block was pressed into a sheet and placed on top of the array membrane. The vacuum pump and heating device were activated, and the temperature was raised to 153°C, slightly above the melting point of indium-tin alloy. The temperature was maintained for 10 minutes, allowing the alloy to melt and spread across the array membrane surface. A hydraulic pressure of approximately 40 MPa was then applied to inject the alloy into the nanotube array membrane. After cooling to room temperature, the remaining alloy was stripped from the membrane surface, and the alumina nanotube array membrane was then ultrasonically cleaned.

[0023] The film was placed in a 10 wt.% NaOH aqueous solution for template etching for 60 h, ultrasonically cleaned and dried to obtain In 9.45 Sn nanowire arrays.

[0024] In 9.45 Sn nanowire arrays, 5% nickel acetate, and 10 wt.% methacryloyloxysilane aqueous solution were hydrothermally reacted at 200° C. for 2 h, and the product was collected by centrifugation and dried to obtain an ITO / NiO composite material.

[0025] Implementation Case 3:

[0026] A 5cm long square aluminum sheet (purity greater than or equal to 99.9%, thickness 0.2mm) was subjected to conventional mechanical processing to remove the surface oxide layer. The electrolyte was prepared from oxalic acid and deionized water, with an oxalic acid content of 0.3M. The treated aluminum sheet was placed in a reaction device, with the area of the aluminum sheet exposed to the electrolyte being 12.56cm2. The electrolyte temperature was fixed at 5°C in a refrigerator, and a carbon sheet was used as the cathode. Anodization was performed for 0.5h at an anode voltage of 40V to obtain a nanotube array membrane with an average pore size of 60nm and a length of 50μm.

[0027] Preparation of ITO / NiO nanowire arrays: The specific steps are as follows: Place the previously prepared aluminum oxide nanotube array film face up in a vacuum hydraulic device, and then place the metal In 9.45 A Sn alloy block was pressed into a sheet and placed on top of the array membrane. The vacuum pump and heating device were activated, and the temperature was raised to 170°C, slightly above the melting point of indium-tin alloy. The temperature was maintained for 10 minutes, allowing the alloy to melt and spread across the array membrane surface. A hydraulic pressure of approximately 40 MPa was then applied to inject the alloy into the nanotube array membrane. After cooling to room temperature, the remaining alloy was stripped from the membrane surface, and the alumina nanotube array membrane was then ultrasonically cleaned.

[0028] The membrane was placed in a 15 wt.% NaOH aqueous solution for template etching for 55 h, ultrasonically cleaned and dried to obtain In 9.45 Sn nanowire arrays.

[0029] In 9.45 Sn nanowire arrays, 1 wt.% nickel nitrate, and 2 wt.% mercaptopropyltrimethoxysilane aqueous solution were hydrothermally reacted at 150° C. for 2 h, and the product was collected by centrifugation and dried to obtain an ITO / NiO composite material.

[0030] Implementation Case 3:

[0031] A 5cm square aluminum sheet (purity greater than or equal to 99.9%, thickness 0.2mm) was machined to remove the surface oxide layer. The electrolyte was prepared from oxalic acid and deionized water, with an oxalic acid content of 0.3M. The treated aluminum sheet was placed in the reaction apparatus, with the area of the aluminum sheet exposed to the electrolyte being 12.56cm. 2 The electrolyte temperature was fixed at 5°C in a refrigerator, and a carbon sheet was used as the cathode. Anodization was performed at an anode voltage of 50 V for 1 h to obtain a nanotube array membrane with an average pore size of 80 nm and a length of 80 μm.

[0032] Preparation of ITO / NiO nanowire arrays: The specific steps are as follows: Place the previously prepared aluminum oxide nanotube array film face up in a vacuum hydraulic device, and then place the metal In 9.45 A Sn alloy block was pressed into a sheet and placed on top of the array membrane. The vacuum pump and heating device were activated, and the temperature was raised to 155°C, slightly above the melting point of indium-tin alloy. The temperature was maintained for 10 minutes, allowing the metal to melt and spread across the array membrane surface. A hydraulic pressure of approximately 40 MPa was then applied to inject the alloy into the nanotube array membrane. After cooling to room temperature, the remaining alloy flakes were peeled off the membrane surface, and the alumina nanotube array membrane was then ultrasonically cleaned.

[0033] The membrane was placed in a 20 wt.% NaOH aqueous solution for template etching for 50 h, ultrasonically cleaned and dried to obtain In 9.45 Sn nanowire arrays.

[0034] Inject metal 9.45 The Sn nanowire array, 5 wt.% nickel nitrate, and 10 wt.% N-methylpyrrolidone aqueous solution were hydrothermally reacted at 150° C. for 2 h, and the product was collected by centrifugation and dried to obtain an ITO / NiO nanowire array.

[0035] Implementation Case 4:

[0036] A 5cm square aluminum sheet (purity greater than or equal to 99.9%, thickness 0.2mm) was machined to remove the surface oxide layer. The electrolyte was prepared from oxalic acid and deionized water, with an oxalic acid content of 0.3M. The treated aluminum sheet was placed in the reaction apparatus, with the area of the aluminum sheet exposed to the electrolyte being 12.56cm. 2The electrolyte temperature was fixed at 5°C in a refrigerator, and a carbon sheet was used as the cathode. Anodization was performed at an anode voltage of 60 V for 2 h to obtain a nanotube array membrane with an average pore size of 100 nm and a length of 200 μm.

[0037] Preparation of ITO / NiO nanowire arrays: The specific steps are as follows: Place the previously prepared aluminum oxide nanotube array film face up in a vacuum hydraulic device, and then place the metal In 9.45 A Sn alloy block was pressed into a sheet and placed on top of the array membrane. The vacuum pump and heating device were activated, and the temperature was raised to 165°C, slightly above the melting point of indium-tin alloy. The temperature was maintained for 5 minutes, allowing the metal to melt and spread across the array membrane surface. A hydraulic pressure of approximately 40 MPa was then applied to inject the alloy into the nanotube array membrane. After cooling to room temperature, the remaining alloy flakes were peeled off the membrane surface, and the alumina nanotube array membrane was then ultrasonically cleaned.

[0038] The membrane was placed in a 25 wt.% NaOH aqueous solution for template etching for 45 h, ultrasonically cleaned and dried to obtain In 9.45 Sn nanowire arrays.

[0039] Inject metal 9.45 Sn nanowire arrays, 5 wt.% nickel sulfate, 2 wt.% N-methylpyrrolidone and 5 wt.% ethylenediaminetetraacetic acid aqueous solution were hydrothermally reacted at 200°C for 2 h, and the product was collected by centrifugation and dried to obtain ITO / NiO nanowire arrays.

[0040] Implementation Case 5:

[0041] A 5cm square aluminum sheet (purity greater than or equal to 99.9%, thickness 0.2mm) was machined to remove the surface oxide layer. The electrolyte was prepared from oxalic acid and deionized water, with an oxalic acid content of 0.3M. The treated aluminum sheet was placed in the reaction apparatus, with the area of the aluminum sheet exposed to the electrolyte being 12.56cm. 2 The electrolyte temperature was fixed at 5°C in a refrigerator, and a carbon sheet was used as the cathode. Anodization was performed at an anode voltage of 100 V for 5 h to obtain a nanotube array membrane with an average pore size of 150 nm and a length of 300 μm.

[0042] Preparation of ITO / Co3O4 nanowire arrays: The specific steps are as follows: Place the previously prepared aluminum oxide nanotube array film face up in a vacuum hydraulic device, and then place the metal In 9.45A Sn alloy block was pressed into a sheet and placed on top of the array membrane. The vacuum pump and heating device were activated, and the temperature was raised to 158°C, slightly above the melting point of indium-tin alloy. The temperature was maintained for 10 minutes, allowing the metal to melt and spread across the array membrane surface. A hydraulic pressure of approximately 40 MPa was then applied to inject the alloy into the nanotube array membrane. After cooling to room temperature, the remaining alloy flakes were peeled off the membrane surface, and the alumina nanotube array membrane was then ultrasonically cleaned.

[0043] The membrane was placed in a 30 wt.% NaOH aqueous solution for template etching for 48 h, ultrasonically cleaned and dried to obtain In 9.45 Sn nanowire arrays.

[0044] Inject metal 9.45 Sn nanowire arrays, 5 wt.% cobalt chloride, and 1 wt.% disodium ethylenediaminetetraacetic acid aqueous solution were hydrothermally reacted at 130° C. for 2 h, and the product was collected by centrifugation and dried to obtain ITO / Co 3 O 4 nanowire arrays.

[0045] Implementation Case 6:

[0046] A 5cm square aluminum sheet (purity greater than or equal to 99.9%, thickness 0.2mm) was machined to remove the surface oxide layer. The electrolyte was prepared from oxalic acid and deionized water, with an oxalic acid content of 0.5M. The treated aluminum sheet was placed in the reaction apparatus, with an area of 12.56cm exposed to the electrolyte. 2 The electrolyte temperature was fixed at 5°C in a refrigerator, and a carbon sheet was used as the cathode. Anodization was performed at an anode voltage of 180 V for 6 h to obtain a nanotube array membrane with an average pore size of 200 nm and a length of 500 μm.

[0047] Preparation of ITO / Co3O4 nanowire arrays: The specific steps are as follows: Place the previously prepared aluminum oxide nanotube array film face up in a vacuum hydraulic device, and then place the metal In 9.45 A Sn alloy block was pressed into a sheet and placed on top of the array membrane. The vacuum pump and heating device were activated, and the temperature was raised to 168°C, slightly above the melting point of indium-tin alloy. The temperature was maintained for 5 minutes, allowing the metal to melt and spread across the array membrane surface. A hydraulic pressure of approximately 45 MPa was then applied to inject the alloy into the nanotube array membrane. After cooling to room temperature, the remaining alloy flakes were peeled off the membrane surface, and the alumina nanotube array membrane was then ultrasonically cleaned.

[0048] The membrane was placed in a 40 wt.% NaOH aqueous solution for template etching for 35 h, ultrasonically cleaned and dried to obtain In 9.45 Sn nanowire arrays.

[0049] Inject metal 9.45Sn nanowire arrays, 5 wt.% cobalt acetate, and 3 wt.% tetrasodium ethylenediaminetetraacetic acid aqueous solution were hydrothermally reacted at 100° C. for 2 h, and the product was collected by centrifugation and dried to obtain ITO / Co 3 O 4 nanowire arrays.

[0050] Implementation Case 7:

[0051] A 5cm square aluminum sheet (purity greater than or equal to 99.9%, thickness 0.2mm) was machined to remove the surface oxide layer. The electrolyte was prepared from oxalic acid and deionized water, with an oxalic acid content of 0.3M. The treated aluminum sheet was placed in the reaction apparatus, with the area of the aluminum sheet exposed to the electrolyte being 12.56cm. 2 The electrolyte temperature was fixed at 5°C in a refrigerator, and a carbon sheet was used as the cathode. Anodization was performed at an anode voltage of 180 V for 6 h to obtain a nanotube array membrane with an average pore size of 200 nm and a length of 500 μm.

[0052] Preparation of ITO / Co3O4 nanowire arrays: The specific steps are as follows: Place the previously prepared aluminum oxide nanotube array film face up in a vacuum hydraulic device, and then place the metal In 9.45 A Sn alloy block was pressed into a sheet and placed on top of the array membrane. The vacuum pump and heating device were activated, and the temperature was raised to 170°C, slightly above the melting point of indium-tin alloy, for 8 minutes. The metal melted and spread across the array membrane surface. A hydraulic pressure of approximately 45 MPa was then applied to inject the alloy into the nanotube array membrane. After cooling to room temperature, the remaining alloy flakes were peeled off the membrane surface, and the alumina nanotube array membrane was then ultrasonically cleaned.

[0053] The membrane was placed in a 50 wt.% NaOH aqueous solution for template etching for 24 h, ultrasonically cleaned and dried to obtain In 9.45 Sn nanowire arrays.

[0054] Inject metal 9.45 Sn nanowire arrays, 5 wt.% cobalt nitrate, and 4 wt.% acrylonitrile aqueous solution were hydrothermally reacted at 110° C. for 2 h, and the product was collected by centrifugation and dried to obtain ITO / Co3O4 nanowire arrays.

[0055] Implementation Case 8:

[0056] A 5cm square aluminum sheet (purity greater than or equal to 99.9%, thickness 0.2mm) was machined to remove the surface oxide layer. The electrolyte was prepared from oxalic acid and deionized water, with an oxalic acid content of 0.3M. The treated aluminum sheet was placed in the reaction apparatus, with the area of the aluminum sheet exposed to the electrolyte being 12.56cm. 2The electrolyte temperature was fixed at 5°C in a refrigerator, and a carbon sheet was used as the cathode. Anodization was performed at an anode voltage of 100 V for 5 h to obtain a nanotube array membrane with an average pore size of 150 nm and a length of 300 μm.

[0057] Preparation of ITO / Co3O4 nanowire arrays: The specific steps are as follows: Place the previously prepared aluminum oxide nanotube array film face up in a vacuum hydraulic device, and then place the metal In 9.45 A Sn alloy block was pressed into a sheet and placed on top of the array membrane. The vacuum pump and heating device were activated, and the temperature was raised to 160°C, slightly above the melting point of indium-tin alloy, for 8 minutes. The metal melted and spread across the array membrane surface. A hydraulic pressure of approximately 48 MPa was then applied to inject the alloy into the nanotube array membrane. After cooling to room temperature, the remaining alloy flakes were peeled off the membrane surface, and the alumina nanotube array membrane was then ultrasonically cleaned.

[0058] The film was placed in a 3 wt.% phosphoric acid and 1 wt.% chromic acid aqueous solution for 72 h to etch the template, and then ultrasonically cleaned and dried to obtain In 9.45 Sn nanowire arrays.

[0059] Inject metal 9.45 Sn nanowire arrays, 5 wt.% cobalt sulfate, and 5 wt.% polyethylene glycol-200 aqueous solution were hydrothermally reacted at 110° C. for 2 h, and the product was collected by centrifugation and dried to obtain ITO / Co 3 O 4 nanowire arrays.

[0060] Implementation Case 9:

[0061] A 5cm square aluminum sheet (purity greater than or equal to 99.9%, thickness 0.2mm) was machined to remove the surface oxide layer. The electrolyte was prepared from oxalic acid and deionized water, with an oxalic acid content of 0.3M. The treated aluminum sheet was placed in the reaction apparatus, with the area of the aluminum sheet exposed to the electrolyte being 12.56cm. 2 The electrolyte temperature was fixed at 5°C in a refrigerator, and a carbon sheet was used as the cathode. Anodization was performed at an anode voltage of 50 V for 1 h to obtain a nanotube array membrane with an average pore size of 80 nm and a length of 80 μm.

[0062] Preparation of ITO / Fe2O3 nanowire arrays: The specific steps are as follows: Place the previously prepared aluminum oxide nanotube array film face up in a vacuum hydraulic device, and then place the metal In 9.45A Sn alloy block was pressed into a sheet and placed on top of the array membrane. The vacuum pump and heating device were activated, and the temperature was raised to 158°C, slightly above the melting point of indium-tin alloy. The temperature was maintained for 8 minutes, allowing the metal to melt and spread across the array membrane surface. A hydraulic pressure of approximately 47 MPa was then applied to inject the alloy into the nanotube array membrane. After cooling to room temperature, the remaining alloy flakes were peeled off the membrane surface, and the alumina nanotube array membrane was then ultrasonically cleaned.

[0063] The film was placed in a 5wt.% phosphoric acid and 2wt.% chromic acid aqueous solution for 60h to etch the template, and then ultrasonically cleaned and dried to obtain In 9.45 Sn nanowire arrays.

[0064] Inject metal 9.45 Sn nanowire arrays, 5wt.% ferric chloride, and 8wt.% polyethylene glycol-400 aqueous solution were hydrothermally reacted at 170°C for 2h, and the product was collected by centrifugation and dried to obtain ITO / Fe2O3 nanowire arrays.

[0065] Implementation Case 10:

[0066] A 5cm square aluminum sheet (purity greater than or equal to 99.9%, thickness 0.2mm) was machined to remove the surface oxide layer. The electrolyte was prepared from oxalic acid and deionized water, with an oxalic acid content of 0.3M. The treated aluminum sheet was placed in the reaction apparatus, with the area of the aluminum sheet exposed to the electrolyte being 12.56cm. 2 The electrolyte temperature was fixed at 5°C in a refrigerator, and a carbon sheet was used as the cathode. Anodization was performed at an anode voltage of 180 V for 6 h to obtain a nanotube array membrane with an average pore size of 200 nm and a length of 500 μm.

[0067] Preparation of ITO / Fe2O3 nanowire arrays: The specific steps are as follows: Place the previously prepared aluminum oxide nanotube array film face up in a vacuum hydraulic device, and then place the metal In 9.45 A Sn alloy block was pressed into a sheet and placed on top of the array membrane. The vacuum pump and heating device were activated, and the temperature was raised to 165°C, slightly above the melting point of indium-tin alloy, for 8 minutes. The metal melted and spread across the array membrane surface. A hydraulic pressure of approximately 45 MPa was then applied to inject the alloy into the nanotube array membrane. After cooling to room temperature, the remaining alloy flakes were peeled off the membrane surface, and the alumina nanotube array membrane was then ultrasonically cleaned.

[0068] The film was placed in an 8 wt.% phosphoric acid and 2 wt.% chromic acid aqueous solution for 50 h to etch the template, and then ultrasonically cleaned and dried to obtain In 9.45 Sn nanowire arrays.

[0069] Inject metal 9.45Sn nanowire arrays, 3wt.% ferric acetate, and 10wt.% disodium ethylenediaminetetraacetic acid aqueous solution were hydrothermally reacted at 170°C for 2h, and the product was collected by centrifugation and dried to obtain ITO / Fe2O3 nanowire arrays.

[0070] Implementation Case 11:

[0071] A 5cm square aluminum sheet (purity greater than or equal to 99.9%, thickness 0.2mm) was machined to remove the surface oxide layer. The electrolyte was prepared from oxalic acid and deionized water, with an oxalic acid content of 0.3M. The treated aluminum sheet was placed in the reaction apparatus, with the area of the aluminum sheet exposed to the electrolyte being 12.56cm. 2 The electrolyte temperature was fixed at 5°C in a refrigerator, and a carbon sheet was used as the cathode. Anodization was performed at an anode voltage of 100 V for 5 h to obtain a nanotube array membrane with an average pore size of 150 nm and a length of 300 μm.

[0072] Preparation of ITO / Fe2O3 nanowire arrays: The specific steps are as follows: Place the previously prepared aluminum oxide nanotube array film face up in a vacuum hydraulic device, and then place the metal In 9.45 A Sn alloy block was pressed into a sheet and placed on top of the array membrane. The vacuum pump and heating device were activated, and the temperature was raised to 170°C, slightly above the melting point of indium-tin alloy. The temperature was maintained for 7 minutes, allowing the metal to melt and spread across the array membrane surface. A hydraulic pressure of approximately 59 MPa was then applied to inject the alloy into the nanotube array membrane. After cooling to room temperature, the remaining alloy flakes were peeled off the membrane surface, and the alumina nanotube array membrane was then ultrasonically cleaned.

[0073] The film was placed in a 10 wt.% phosphoric acid and 1 wt.% chromic acid aqueous solution for template etching for 55 h, ultrasonically cleaned and dried to obtain In 9.45 Sn nanowire arrays.

[0074] Inject metal 9.45 Sn nanowire arrays, 3wt.% ferric nitrate, 1wt.% disodium ethylenediaminetetraacetic acid solution and 3wt.% mercaptopropyltrimethoxysilane were hydrothermally reacted at 170°C for 2h, and the product was collected by centrifugation and dried to obtain ITO / Fe2O3 nanowire arrays.

[0075] Implementation Case 12:

[0076] A 5cm square aluminum sheet (purity greater than or equal to 99.9%, thickness 0.2mm) was machined to remove the surface oxide layer. The electrolyte was prepared from oxalic acid and deionized water, with an oxalic acid content of 0.3M. The treated aluminum sheet was placed in the reaction apparatus, with the area of the aluminum sheet exposed to the electrolyte being 12.56cm. 2The electrolyte temperature was fixed at 5°C in a refrigerator, and a carbon sheet was used as the cathode. Anodization was performed at an anode voltage of 40 V for 0.3 h to obtain a nanotube array membrane with an average pore size of 40 nm and a length of 30 μm.

[0077] Preparation of ITO / Fe2O3 nanowire arrays: The specific steps are as follows: Place the previously prepared aluminum oxide nanotube array film face up in a vacuum hydraulic device, and then place the metal In 9.45 A Sn alloy block was pressed into a sheet and placed on top of the array membrane. The vacuum pump and heating device were activated, and the temperature was raised to 155°C, slightly above the melting point of indium-tin alloy. The temperature was maintained for 7 minutes, allowing the metal to melt and spread across the array membrane surface. A hydraulic pressure of approximately 60 MPa was then applied to inject the alloy into the nanotube array membrane. After cooling to room temperature, the remaining alloy flakes were peeled off the membrane surface, and the alumina nanotube array membrane was then ultrasonically cleaned.

[0078] The film was placed in a 10 wt.% phosphoric acid and 2 wt.% chromic acid aqueous solution for 48 h to etch the template, and then ultrasonically cleaned and dried to obtain In 9.45 Sn nanowire arrays.

[0079] Inject metal 9.45 Sn nanowire arrays, 3wt.% ferric sulfate, and 2wt.% polyvinyl pyrrolidone aqueous solution were hydrothermally reacted at 180°C for 2h, and the product was collected by centrifugation and dried to obtain ITO / Fe2O3 nanowire arrays.

[0080] Implementation Case 13:

[0081] A 5cm square aluminum sheet (purity greater than or equal to 99.9%, thickness 0.2mm) was machined to remove the surface oxide layer. The electrolyte was prepared from oxalic acid and deionized water, with an oxalic acid content of 0.3M. The treated aluminum sheet was placed in the reaction apparatus, with the area of the aluminum sheet exposed to the electrolyte being 12.56cm. 2 The electrolyte temperature was fixed at 5°C in a refrigerator, and a carbon sheet was used as the cathode. Anodization was performed at an anode voltage of 180 V for 6 h to obtain a nanotube array membrane with an average pore size of 200 nm and a length of 500 μm.

[0082] Preparation of ITO / CuO nanowire arrays: The specific steps are as follows: Place the previously prepared aluminum oxide nanotube array film face up in a vacuum hydraulic device, and then place the metal In 9.45A Sn alloy block was pressed into a sheet and placed on top of the array membrane. The vacuum pump and heating device were activated, and the temperature was raised to 155°C, slightly above the melting point of indium-tin alloy. The temperature was maintained for 8 minutes, allowing the metal to melt and spread across the array membrane surface. A hydraulic pressure of approximately 45 MPa was then applied to inject the alloy into the nanotube array membrane. After cooling to room temperature, the remaining alloy flakes were peeled off the membrane surface, and the alumina nanotube array membrane was then ultrasonically cleaned.

[0083] The film was placed in a 10 wt.% phosphoric acid and 3 wt.% chromic acid aqueous solution for 48 h to etch the template, and then ultrasonically cleaned and dried to obtain In 9.45 Sn nanowire arrays.

[0084] Inject metal 9.45 Sn nanowire arrays, 3 wt.% copper sulfate, and 3 wt.% acrylonitrile aqueous solution were hydrothermally reacted at 190° C. for 2 h, and the product was collected by centrifugation and dried to obtain ITO / CuO nanowire arrays.

[0085] Implementation Case 14:

[0086] A 5cm square aluminum sheet (purity greater than or equal to 99.9%, thickness 0.2mm) was machined to remove the surface oxide layer. The electrolyte was prepared from oxalic acid and deionized water, with an oxalic acid content of 0.3M. The treated aluminum sheet was placed in the reaction apparatus, with the area of the aluminum sheet exposed to the electrolyte being 12.56cm. 2 The electrolyte temperature was fixed at 5°C in a refrigerator, and a carbon sheet was used as the cathode. Anodization was performed at an anode voltage of 180 V for 6 h to obtain a nanotube array membrane with an average pore size of 200 nm and a length of 500 μm.

[0087] Preparation of ITO / CuO nanowire arrays: The specific steps are as follows: Place the previously prepared aluminum oxide nanotube array film face up in a vacuum hydraulic device, and then place the metal In 9.45 A Sn alloy block was pressed into a sheet and placed on top of the array membrane. The vacuum pump and heating device were activated, and the temperature was raised to 165°C, slightly above the melting point of indium-tin alloy. The temperature was maintained for 7 minutes, allowing the metal to melt and spread across the array membrane surface. A hydraulic pressure of approximately 55 MPa was then applied to inject the alloy into the nanotube array membrane. After cooling to room temperature, the remaining alloy flakes were peeled off the membrane surface, and the alumina nanotube array membrane was then ultrasonically cleaned.

[0088] The membrane was placed in a 50 wt.% NaOH aqueous solution for template etching for 24 h, ultrasonically cleaned and dried to obtain In 9.45 Sn nanowire arrays.

[0089] Inject metal 9.45Sn nanowire arrays, 3 wt.% copper chloride, and 10 wt.% polyethylene glycol-200 aqueous solution were hydrothermally reacted at 190° C. for 2 h, and the product was collected by centrifugation and dried to obtain ITO / CuO nanowire arrays.

[0090] Implementation Case 15:

[0091] A 5cm square aluminum sheet (purity greater than or equal to 99.9%, thickness 0.2mm) was machined to remove the surface oxide layer. The electrolyte was prepared from oxalic acid and deionized water, with an oxalic acid content of 0.3M. The treated aluminum sheet was placed in the reaction apparatus, with the area of the aluminum sheet exposed to the electrolyte being 12.56cm. 2 The electrolyte temperature was fixed at 5°C in a refrigerator, and a carbon sheet was used as the cathode. Anodization was performed at an anode voltage of 50 V for 1 h to obtain a nanotube array membrane with an average pore size of 80 nm and a length of 80 μm.

[0092] Preparation of ITO / Ag2O nanowire arrays: The specific steps are as follows: Place the previously prepared aluminum oxide nanotube array film face up in a vacuum hydraulic device, and then place the metal In 9.45 A Sn alloy block was pressed into a sheet and placed on top of the array membrane. The vacuum pump and heating device were activated, and the temperature was raised to 160°C, slightly above the melting point of indium-tin alloy. The temperature was maintained for 10 minutes, allowing the metal to melt and spread across the array membrane surface. A hydraulic pressure of approximately 50 MPa was then applied to inject the alloy into the nanotube array membrane. After cooling to room temperature, the remaining alloy flakes were peeled off the membrane surface, and the alumina nanotube array membrane was then ultrasonically cleaned.

[0093] The membrane was placed in a 30 wt.% NaOH aqueous solution for template etching for 48 h, ultrasonically cleaned and dried to obtain In 9.45 Sn nanowire arrays.

[0094] Inject metal 9.45 Sn nanowire arrays, 3 wt.% silver nitrate, and 5 wt.% polyethylene glycol-400 aqueous solution were hydrothermally reacted at 100° C. for 2 h, and the product was collected by centrifugation and dried to obtain ITO / Ag2O nanowire arrays.

[0095] Implementation Case 16:

[0096] A 5cm square aluminum sheet (purity greater than or equal to 99.9%, thickness 0.2mm) was machined to remove the surface oxide layer. The electrolyte was prepared from oxalic acid and deionized water, with an oxalic acid content of 0.3M. The treated aluminum sheet was placed in the reaction apparatus, with the area of the aluminum sheet exposed to the electrolyte being 12.56cm. 2The electrolyte temperature was fixed at 5°C in a refrigerator, and a carbon sheet was used as the cathode. Anodization was performed at an anode voltage of 100 V for 5 h to obtain a nanotube array membrane with an average pore size of 150 nm and a length of 300 μm.

[0097] Preparation of ITO / RuO2 nanowire arrays: The specific steps are as follows: Place the previously prepared aluminum oxide nanotube array film face up in a vacuum hydraulic device, and then place the metal In 9.45 A Sn alloy block was pressed into a sheet and placed on top of the array membrane. The vacuum pump and heating device were activated, and the temperature was raised to 165°C, slightly above the melting point of indium-tin alloy. The temperature was maintained for 5 minutes, allowing the metal to melt and spread across the array membrane surface. A hydraulic pressure of approximately 40 MPa was then applied to inject the alloy into the nanotube array membrane. After cooling to room temperature, the remaining alloy flakes were peeled off the membrane surface, and the alumina nanotube array membrane was then ultrasonically cleaned.

[0098] The membrane was placed in a 5 wt.% NaOH aqueous solution for template etching for 72 h, ultrasonically cleaned and dried to obtain In 9.45 Sn nanowire arrays.

[0099] Inject metal 9.45 Sn nanowire arrays, 7wt.% ruthenium chloride, and 6wt.% polyvinyl pyrrolidone aqueous solution were hydrothermally reacted at 150°C for 2h, and the product was collected by centrifugation and dried to obtain ITO / RuO2 nanowire arrays.

[0100] Implementation Case 17:

[0101] A 5cm square aluminum sheet (purity greater than or equal to 99.9%, thickness 0.2mm) was machined to remove the surface oxide layer. The electrolyte was prepared from oxalic acid and deionized water, with an oxalic acid content of 0.3M. The treated aluminum sheet was placed in the reaction apparatus, with the area of the aluminum sheet exposed to the electrolyte being 12.56cm. 2 The electrolyte temperature was fixed at 5°C in a refrigerator, and a carbon sheet was used as the cathode. Anodization was performed at an anode voltage of 20 V for 0.05 h to obtain a nanotube array membrane with an average pore size of 10 nm and a length of 1 μm.

[0102] Preparation of ITO / PtO2 nanowire arrays: The specific steps are as follows: Place the previously prepared aluminum oxide nanotube array film face up in a vacuum hydraulic device, and then place the metal In 9.45 A Sn alloy block is pressed into a sheet and placed on top of the array membrane. The vacuum pump and heating device are activated, and the temperature is raised to 170°C (slightly above the melting point of indium-tin alloy) for 5-10 minutes. The metal melts and spreads across the array membrane surface. A hydraulic pressure of approximately 60 MPa is then applied to inject the alloy into the nanotube array membrane. After cooling to room temperature, the remaining alloy flakes are peeled off the membrane surface, and the alumina nanotube array membrane is then ultrasonically cleaned.

[0103] The film was placed in a sulfur hexafluoride plasma cleaning apparatus for template etching at a power of 40kW for 24 hours. After the reaction, metal In was obtained. 9.45 Sn nanowire arrays.

[0104] Inject metal 9.45 Sn nanowire arrays, 7 wt.% chloroplatinic acid, and 8 wt.% hexadecyltrimethylammonium bromide aqueous solution were hydrothermally reacted at 140° C. for 2 h, and the product was collected by centrifugation and dried to obtain ITO / PtO2 nanowire arrays.

Claims

1. A method for preparing an ITO nanowire composite material, characterized in that The method proceeds as follows: (1) Using the secondary anodic aluminum oxide film as a template, the physical hydraulic method was used to 9.45 The Sn alloy is pressed into the secondary anodic aluminum oxide film template at a temperature 5-20 °C above its melting point; after cooling, the secondary anodic aluminum oxide film template is placed in a (5-30) wt.% NaOH solution or an aqueous solution of (3-10) wt.% phosphoric acid and (1-3) wt.% chromic acid to dissolve and remove the template, and then ultrasonically cleaned and dried in an oven to obtain In 9.45 Sn nanowires; (2) The In prepared in (1) 9.45 Sn nanowires, (1-10) wt.% soluble organic matter, and (1-5) wt.% metal ion salts were added to an aqueous solution and reacted under hydrothermal conditions at 120-200 ºC for 2 h to obtain an ITO nanowire / metal oxide composite material.

2. The preparation method according to claim 1, characterized in that: The diameter of the secondary anodic aluminum oxide film template is 10-500nm and the length is 1-500µm.

3. The preparation method according to claim 1, characterized in that: The soluble organic matter is one or more selected from the group consisting of hexadecyltrimethylammonium bromide, methacryloxysilane, mercaptopropyltrimethoxysilane, N-methylpyrrolidone, ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, tetrasodium ethylenediaminetetraacetate, acrylonitrile, polyethylene glycol-200, polyethylene glycol-400, and polyvinylpyrrolidone.

4. The preparation method according to claim 1, characterized in that: The metal ion salt is one selected from the group consisting of nickel chloride, nickel acetate, nickel nitrate, nickel sulfate, cobalt chloride, cobalt acetate, cobalt nitrate, cobalt sulfate, ferric chloride, ferric acetate, ferric nitrate, ferric sulfate, copper sulfate, copper chloride, silver nitrate, ruthenium chloride, and chloroplatinic acid.

5. The preparation method according to claim 1, characterized in that: The metal oxide is one selected from the group consisting of nickel oxide, cobalt oxide, iron oxide, copper oxide, silver oxide, ruthenium oxide, and platinum oxide.