阅读说明：本技术 一种在TiO2纳米管上制备纳米银的方法 (In TiO2Method for preparing nano silver on nano tube ) 是由 陈超 神瑶 贺图升 田长安 王操 于 2021-07-23 设计创作，主要内容包括：一种在TiO-2纳米管上制备纳米银的方法,涉及利用电化学方法制备纳米材料技术领域。采用电化学沉积法,以硝酸银作为银源,硼酸为稳定剂,TiO-2纳米管为基体作为工作电极,铂金属作为对电极,Ag/AgCl电极作为参比电极,采用脉冲电沉积法在TiO-2纳米管表面制备纳米银；通过改变溶液的浓度、脉冲电压、脉冲时间、间隔时间以及循环次数实现纳米银形貌和尺寸的调节。通过添加硼酸作为稳定剂,通过电化学沉积法一次性在TiO-2纳米管表面制备片状或颗粒状纳米银。通过改变溶液的浓度、脉冲电压、脉冲时间、间隔时间以及循环次数实现纳米银形貌和尺寸的调节,通过实验发现这些参数对制备纳米银材料的形貌和颗粒大小是十分关键的。(In TiO 2 A method for preparing nano silver on a nanotube relates to the technical field of preparing nano materials by an electrochemical method. Adopting electrochemical deposition method, using silver nitrate as silver source, using boric acid as stabilizing agent and using TiO 2 The nanotube is used as a working electrode, platinum metal is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, and a pulse electrodeposition method is adopted to deposit on TiO 2 Preparing nano silver on the surface of the nanotube; the shape and size of the nano-silver can be adjusted by changing the concentration of the solution, the pulse voltage, the pulse time, the interval time and the cycle number. By adding boric acid as stabilizer, and performing electrochemical deposition on TiO at one time 2 Preparation of flakes or particles on nanotube surfacesForm nano silver. The shape and size of the nano-silver can be adjusted by changing the concentration, pulse voltage, pulse time, interval time and cycle number of the solution, and experiments show that the parameters are very critical to the shape and particle size of the nano-silver material.)

1. In TiO₂The method for preparing nano silver on the nano tube adopts an electrochemical deposition method and is characterized in that silver nitrate is used as a silver source, boric acid is used as a stabilizer, and TiO is used as a stabilizer₂The nanotube is used as a working electrode, platinum metal is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, and a pulse electrodeposition method is adopted to deposit on TiO₂Preparing nano silver on the surface of the nanotube; the shape and size of the nano-silver can be adjusted by changing the concentration of the solution, the pulse voltage, the pulse time, the interval time and the cycle number.

2. The method of claim 1, characterized by the steps of:

arranging electrodes

Electrodes arranged in the container and made of TiO₂The nanotube is used as a working electrode, the platinum metal is used as a counter electrode, the Ag/AgCl electrode is used as a reference electrode, and the nano-tube and the reference electrode are respectively connected with electricityConnecting each corresponding electrode of the chemical workstation;

② preparing solution

Dissolving boric acid in deionized water to prepare a boric acid solution with the concentration of 0.01-0.05 mol/L, dissolving silver nitrate in the deionized water in a darkroom to prepare a silver nitrate solution with the concentration of 0.01-0.5 mol/L, quickly and uniformly mixing the two solutions according to the volume ratio of 1: 1, and pouring the mixture into a container prepared with an electrode;

pulse electrodeposition

Setting pulse voltage to be-0.4 to-1.0V, pulse time to be 0.5 to 1.0s, interval time to be 1 to 4s, and circulating for 10 to 200 times;

fourthly, cleaning and drying

After the pulse electrodeposition is finished, taking out the TiO₂Washing the nano tube with deionized water, and drying to obtain the nano tube₂And preparing nano silver on the nano tube.

3. The method of claim 2, characterized by the steps of:

arranging electrodes

Electrodes arranged in the container and made of TiO₂The nanotube is used as a substrate as a working electrode, platinum metal as a counter electrode and an Ag/AgCl electrode as a reference electrode, and is respectively connected with each corresponding electrode of the electrochemical workstation;

② preparing solution

Dissolving boric acid in deionized water to prepare a boric acid solution with the concentration of 0.01mol/L, dissolving silver nitrate in the deionized water in a darkroom to prepare a silver nitrate solution with the concentration of 0.01mol/L, quickly and uniformly mixing the two solutions according to the volume ratio of 1: 1, and pouring the two solutions into a container prepared with an electrode;

pulse electrodeposition

Setting pulse voltage to-0.8V, pulse time to 1.0s, interval time to 2s, and circulating for 20 times;

fourthly, cleaning and drying

After the pulse electrodeposition is finished, taking out the TiO₂Washing the nano tube with deionized water, and drying to obtain the nano tube₂Preparing the flaky nano silver on the nano tube.

4. The method of claim 2, characterized by the steps of:

arranging electrodes

Electrodes arranged in the container and made of TiO₂The nanotube is used as a substrate as a working electrode, platinum metal as a counter electrode and an Ag/AgCl electrode as a reference electrode, and is respectively connected with each corresponding electrode of the electrochemical workstation;

② preparing solution

Dissolving boric acid in deionized water to prepare a boric acid solution with the concentration of 0.01mol/L, dissolving silver nitrate in the deionized water in a darkroom to prepare a silver nitrate solution with the concentration of 0.01mol/L, quickly and uniformly mixing the two solutions according to the volume ratio of 1: 1, and pouring the two solutions into a container prepared with an electrode;

pulse electrodeposition

Setting pulse voltage to be-1.0V, pulse time to be 1.0s, interval time to be 3s, and circulating for 120 times;

fourthly, cleaning and drying

After the pulse electrodeposition is finished, taking out the TiO₂Washing the nano tube with deionized water, and drying to obtain the nano tube₂Preparing granular nano silver on the nano tube.

5. The method of any one of claims 1 to 4, wherein the TiO is₂The preparation method of the nanotube comprises the following steps: putting the Ti sheet into ammonium chloride and ethylene glycol solution, introducing 40V direct current power supply for 3h, washing with deionized water after the completion, and drying to prepare the orderly-arranged TiO on the Ti sheet₂An array of nanotubes.

Technical Field

The invention relates to the technical field of preparing nano materials by an electrochemical method, in particular to a method for preparing a nano material on TiO₂A method for preparing nano silver on a nano tube.

Background

With the continuous development of scientific technology, new materials with unique purposes are developed, and meanwhile, the preparation technology of the materials is required to advance with time, and the preparation method of the traditional materials has certain difficulty in preparing uniform nano materials on uneven surfaces, so researchers are continuously searching for new processes and new methods, wherein the electrochemical deposition technology is particularly concerned.

Electrochemical deposition is a typical additive manufacturing process that is formed in a layer-by-layer build-up. The method is a liquid phase method, can obtain surface materials with multiple functions on the surface of the material by an electrochemical deposition technology, is an economic material preparation method, has the advantages of low equipment investment, simple process, easy operation, safe environment and flexible production mode, and is suitable for industrial mass production. However, materials prepared using electrochemical deposition techniques are often microscopically films of a continuous accumulation of particles, and uniform nanomaterials are difficult to prepare because the nucleation and growth rates on the substrate surface are not easily controlled.

TiO₂The nano-tube material has the characteristics of large surface area and regular arrangement, and the preparation of nano-silver on the surface of the nano-tube material is beneficial to improving TiO₂The performance of the nano tube and the capacity of the nano silver are improved. Meanwhile, the nano silver has better optical and plasma properties, and the properties have important influence on the application of plasma photocatalysis, biosensors, colored glasses spraying and the like. At present in TiO₂The preparation of nano silver on the nanotube is often synthesized in solution by a chemical synthesis method, and the attachment of the nano silver on the surface of the nanotube cannot be effectively realized. Simultaneously, TiO is used according to the traditional electrochemical deposition method₂The preparation of nano-materials with special shapes by using the nano-tube as the matrix surface is also very difficult. Is especially suitable for the treatment of diabetesThe reason for this is precisely the electrochemical deposition method based on TiO₂The generation and growth speed of crystal nucleus on the surface of the nanotube substrate is not easy to control, and effective flaky or granular nano silver cannot be obtained.

Disclosure of Invention

The invention aims to provide a method for preparing TiO₂Method for preparing nano silver on nano tube by adopting electrochemical deposition method to coat TiO at one time₂The method for preparing the flaky or granular nano silver on the surface of the nano tube is simple, and the preparation cost is greatly reduced.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows: in TiO₂The method for preparing nano silver on the nano tube adopts an electrochemical deposition method, takes silver nitrate as a silver source, boric acid as a stabilizer and TiO₂The nanotube is used as a working electrode, platinum metal is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, and a pulse electrodeposition method is adopted to deposit on TiO₂Preparing nano silver on the surface of the nanotube; the shape and size of the nano-silver can be adjusted by changing the concentration of the solution, the pulse voltage, the pulse time, the interval time and the cycle number.

Compared with the prior art, the invention has the beneficial effects that:

firstly, the invention adds boric acid as a stabilizer and adopts an electrochemical deposition method to perform one-step reaction on TiO₂The flaky or granular nano silver is prepared on the surface of the nano tube, thereby overcoming the defect that the conventional preparation technology can not realize the uniform deposition of the flaky or granular nano silver on TiO₂Technical defects of the nanotube surface.

Secondly, the invention realizes the adjustment of the shape and the size of the nano-silver by changing the concentration, the pulse voltage, the pulse time, the interval time and the cycle number of the solution, and experiments show that the parameters are very critical to the shape and the particle size of the prepared nano-silver material.

Thirdly, the invention adopts the electrochemical deposition technology to obviously reduce the preparation cost and the preparation possibility of the Ag nano material, and the prepared Ag nano sheet or nano particle can be firmly attached to the TiO nano particle₂Nanotube-based heterogeneous surface, the electrochemical deposition method being such that the nanotubes are nano-sizedAg and TiO₂The nanotube matrix is attached in one step, thereby simplifying the procedure for preparing the material.

Drawings

FIG. 1 is a schematic representation of example 1 on TiO₂And depositing Ag nano sheets on the surfaces of the nanotubes to prepare SEM images of products.

FIG. 2 shows the results obtained in example 1 in TiO₂And depositing Ag nano sheets on the surfaces of the nano tubes to prepare XRD patterns of products.

FIG. 3 shows the results obtained in example 2 in TiO₂SEM image of product prepared by depositing Ag nano particles on the surface of the nanotube.

FIG. 4 shows the results obtained in example 2 in TiO₂XRD pattern of product prepared by depositing Ag nano particles on the surface of the nano tube.

Detailed Description

Example 1

In TiO₂The method for depositing the Ag nanosheets on the surfaces of the nanotubes comprises the following steps:

preparation of TiO₂Nanotube and method of manufacturing the same

Putting the Ti sheet into ammonium chloride and ethylene glycol solution, introducing 40V direct current power supply for 3h, washing with deionized water after the completion, and drying to prepare the orderly-arranged TiO on the Ti sheet₂An array of nanotubes.

② arranging electrodes

Configuring electrodes in a container to prepare the TiO by the step I₂The Ti sheet of the nanotube is used as a working electrode, platinum metal is used as a counter electrode, and an Ag/AgCl electrode is used as a reference electrode and is respectively connected with each corresponding electrode of the electrochemical workstation.

Preparing solution

0.062g of boric acid is weighed and dissolved in 100mL of deionized water, and the mixture is mixed evenly to prepare a boric acid solution with the concentration of 0.01 mol/L. 0.170g of silver nitrate is weighed in a dark room and dissolved in 100mL of deionized water, and the silver nitrate solution with the concentration of 0.01mol/L is prepared by even mixing. The two solutions were quickly mixed well and poured into a container ready for electrodes.

Pulse electrodeposition

Setting pulse voltage at-0.8V, pulse time at 1.0s, interval time at 2s, and circulating for 20 times.

Fifthly, cleaning and drying

After the pulse electrodeposition is finished, taking out the TiO₂Washing the nano tube with deionized water, and drying to obtain the nano tube₂Preparing the flaky nano silver on the nano tube.

FIGS. 1 and 2 are the TiO molecule of example 1₂SEM images and XRD images of products prepared by depositing Ag nano sheets on the surfaces of the nanotubes. As can be seen from FIG. 1, the hexagonal-like nanosheets grow vertically on TiO₂The surface of the nanotube is mainly composed of Ag and TiO as can be seen from the XRD pattern of FIG. 2₂Shows that Ag is successfully prepared in example 1, and combines the figure 1 and the figure 2 to show that the hexagonally-like Ag nano-plate successfully prepared in example 1 grows vertically to TiO₂The surface of the nanotubes.

Example 2

In TiO₂The method for depositing Ag nano particles on the surface of the nano tube comprises the following steps:

preparation of TiO₂Nanotube and method of manufacturing the same

Putting the Ti sheet into ammonium chloride and ethylene glycol solution, introducing 40V direct current power supply for 3h, washing with deionized water after the completion, and drying to prepare the orderly-arranged TiO on the Ti sheet₂An array of nanotubes.

② arranging electrodes

Configuring electrodes in a container to prepare the TiO by the step I₂The Ti sheet of the nanotube is used as a working electrode, platinum metal is used as a counter electrode, and an Ag/AgCl electrode is used as a reference electrode and is respectively connected with each corresponding electrode of the electrochemical workstation.

Preparing solution

0.062g of boric acid is weighed and dissolved in 100mL of deionized water, and the mixture is mixed evenly to prepare a boric acid solution with the concentration of 0.01 mol/L. 0.170g of silver nitrate is weighed in a dark room and dissolved in 100mL of deionized water, and the silver nitrate solution with the concentration of 0.01mol/L is prepared by even mixing. The two solutions were quickly mixed well and poured into a container ready for electrodes.

Pulse electrodeposition

Setting pulse voltage at-1.0V, pulse time at 1.0s, interval time at 3s, and circulating 120 times.

Fifthly, cleaning and drying

After the pulse electrodeposition is finished, taking out the TiO₂Washing the nano tube with deionized water, and drying to obtain the nano tube₂Preparing granular nano silver on the nano tube.

FIGS. 3 and 4 show examples 2 in TiO, respectively₂SEM image and XRD image of the product prepared by depositing Ag nano particles on the surface of the nanotube. As can be seen from FIG. 3, the nanoparticles are uniformly deposited on the TiO₂The wall and top of the nanotube, FIG. 4 shows that the material is mainly Ag and TiO₂Shows that Ag was successfully prepared in example 2, and shows that Ag was successfully prepared in TiO in example 2 by combining FIG. 3 and FIG. 4₂Ag nano particles are deposited on the surface of the nano tube.

The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.