CN110552028B - A kind of preparation method of antibacterial nanoporous material - Google Patents

Abstract

The invention discloses a preparation method of an antibacterial nanoporous material. The specific process of the method is as follows: firstly, using porous titanium or porous titanium alloy as a cathode, using graphite or platinum sheet as an anode, and using copper sulfate solution as an electrolyte for electrodeposition, The Cu ²⁺ in the electrolyte is deposited on the surface of the porous titanium or the porous titanium alloy, followed by heat treatment and nitric acid leaching in sequence to obtain a nanoporous material. In the method, Cu is first attached and diffused into the porous titanium or porous titanium alloy to form a multi-element alloy, and then the copper in the multi-element alloy is removed by nitric acid leaching to form nano-pores, and at the same time, the oxidation is carried out to form a multi-element alloy on the porous titanium or porous titanium alloy substrate. The needle-shaped nanoporous titanium oxide surface layer is obtained to obtain a nanoporous material. The needle-shaped nanoporous titanium oxide on the surface of the nanoporous material will pierce the surface of the bacteria and generate capillary suction to achieve antibacterial and bactericidal functions and self-cleaning functions.

Description

A kind of preparation method of antibacterial nanoporous material

technical field

The invention belongs to the technical field of medical inorganic antibacterial materials, and particularly relates to a preparation method of an antibacterial nanoporous material.

Background technique

Antibacterial materials are generally divided into two categories, namely organic antibacterial materials and inorganic antibacterial materials. With the rapid development of medical technology in recent years, various effective organic antibacterial materials have been developed. The main varieties of organic antibacterial materials are quaternary ammonium salts, imidazoles, halogens, phenols, etc. Among them, quaternary ammonium antibacterial materials are favored due to their low toxicity, low price, and broad-spectrum antibacterial properties, and are currently the most widely used organic antibacterial materials. However, the safety and stability of organic antibacterial materials have always been an important obstacle to the promotion and application of organic antibacterial materials. At present, inorganic antibacterial materials mainly use the antibacterial ability of metals such as silver, copper, and zinc. First, through a certain preparation method, metals such as silver, copper, zinc (or their ions) are fixed on the surface of the base material to make antibacterial agents, and then they are prepared into corresponding products, that is, materials with antibacterial ability are realized.

Nano antibacterial material is a new type of inorganic antibacterial material that has gradually gained the attention of researchers and developed rapidly in the early 1990s. The material has the function of autonomously inhibiting and killing bacteria. At present, nano-antibacterial materials have problems that sterilization cannot be achieved, and that their surfaces cannot achieve self-cleaning functions during the antibacterial process.

SUMMARY OF THE INVENTION

The technical problem to be solved by the present invention is to provide a preparation method of an antibacterial nanoporous material in view of the above-mentioned deficiencies of the prior art. The method uses electrodeposition and heat treatment in sequence to make Cu adhere and diffuse into porous titanium or porous titanium alloy to form a multi-element alloy, and then use nitric acid to remove copper in the multi-element alloy and form nano-pores, and at the same time, oxidation occurs. A needle-shaped nanoporous titanium oxide surface layer is formed on the porous titanium or porous titanium alloy substrate to obtain a nanoporous material with uniform nanoporous distribution. The surface of the nanoporous material has needle-shaped nanoporous titanium oxide, which will pierce the surface of bacteria and generate capillaries Suction, to achieve antibacterial and sterilization functions, and has a self-cleaning function.

In order to solve the above-mentioned technical problems, the technical scheme adopted in the present invention is: a preparation method of an antibacterial nanoporous material, characterized in that the method comprises the following steps:

Step 1. Use porous titanium or porous titanium alloy as the cathode, graphite or platinum sheet as the anode, and copper sulfate solution with a mass concentration of 10% to 30% as the electrolyte to perform electrodeposition, so that the Cu ²⁺ in the electrolyte Deposited on the surface of porous titanium or porous titanium alloys;

In step 2, the porous titanium or porous titanium alloy with Cu ²⁺ deposited on the surface in step 1 is put into an argon furnace for heat treatment; the temperature of the heat treatment is 300℃～800℃, and the holding time is 1h～5h;

Step 3: Put the heat-treated porous titanium or porous titanium alloy with Cu ²⁺ deposited on the surface into a nitric acid solution for acid leaching to obtain a nanoporous material; the mass concentration of the nitric acid solution is 30% to 60% , the temperature of acid leaching treatment is 30 ℃ ~ 70 ℃.

In the present invention, Cu ²⁺ is firstly deposited on the surface of porous titanium or porous titanium alloy by the method of electrodeposition, so that Cu is evenly distributed on the surface of the porous titanium or porous titanium alloy substrate and forms a tight bond, and then heat treatment is performed to make it adhere to the substrate. The Cu on the surface quickly enters the interior of the base metal through atomic diffusion under high temperature conditions to form a titanium-copper multi-alloy fire-titanium alloy-copper multi-alloy, and then the copper in the multi-alloy is removed by acid leaching. While rapidly diffusing into the base metal, nano-scale diffusion lines are formed in the porous titanium or porous titanium alloy matrix. After acid leaching, the copper in the multi-element alloy is dissolved in nitric acid, leaving nano-pores, so that the porous titanium or porous A nanoporous layer is formed on the surface of the titanium alloy substrate. Since nitric acid is an oxidizing inorganic acid, it has an oxidizing effect on both porous titanium or porous titanium alloy, thereby forming a needle-shaped nanoporous titanium oxide surface layer on the porous titanium or porous titanium alloy substrate. The nanoporous material with uniform distribution of nanoporous pores is obtained; since the surface of the nanoporous material prepared by the present invention has needle-shaped nano-porous titanium oxide, when contacted with bacteria, the needle-shaped nano-porous titanium oxide will pierce the surface of bacteria, thereby realizing antibacterial, In the process of antibacterial and sterilization, the nanoporous structure of needle-shaped nanoporous titanium oxide will generate capillary suction for bacteria, which will actively sterilize and further enhance the antibacterial and bactericidal functions. Under the action of irradiation, the organic matter will be oxidized and decomposed, so as to realize the self-cleaning function in the process of antibacterial and sterilization.

The above-mentioned preparation method of an antibacterial nanoporous material is characterized in that the preparation raw material of the porous titanium in step 1 is titanium powder or titanium fiber, and the preparation raw material of the porous titanium alloy is titanium alloy powder or titanium alloy fiber. Selecting the above-mentioned raw materials to prepare porous titanium or porous titanium alloy with uniform pore distribution is favorable for forming nanoporous materials with uniform nanoporous distribution.

The above-mentioned preparation method of an antibacterial nanoporous material is characterized in that the nanoporous material obtained in step 3 is composed of a porous titanium or a porous titanium alloy matrix and a needle-shaped nanoporous titanium oxide surface layer. The porous base material has a larger specific surface area, which enhances the adhesion of the surface layer on the base and avoids cracking of the surface layer.

Compared with the prior art, the present invention has the following advantages:

1. The present invention adopts electrodeposition and heat treatment in turn to make Cu adhere and diffuse into porous titanium or porous titanium alloy to form a multi-element alloy, and then use nitric acid to carry out acid leaching treatment to remove copper in the multi-element alloy and form nano-holes, and oxidation occurs at the same time. Thus, a needle-shaped nano-porous titanium oxide surface layer is formed on the porous titanium or porous titanium alloy substrate to obtain a nano-porous material with uniform distribution of nano-porosity, and the process is simple and easy to realize.

2. The surface of the nanoporous material prepared by the present invention has needle-shaped nano-porous titanium oxide, which will pierce the surface of bacteria and realize antibacterial and sterilizing functions. Capillary suction, active sterilization, further enhanced antibacterial and sterilization functions.

3. Under the action of UV irradiation, the nanoporous material prepared by the present invention will oxidatively decompose organic matter, so as to realize the self-cleaning function in the process of antibacterial and sterilization.

4. The preparation process of the present invention is simple, the production cost is low, the requirement for production equipment is low, and it is suitable for large-scale industrial production.

The technical solutions of the present invention will be further described in detail below through examples.

Detailed ways

Example 1

This embodiment includes the following steps:

Step 1. Use the porous titanium plate prepared by titanium powder as the cathode, use the graphite as the anode, and use the copper sulfate solution with a mass concentration of 25% as the electrolyte to carry out electrodeposition, so that the Cu ²⁺ in the electrolyte is deposited on the porous titanium plate. s surface;

Step 2: Put the porous titanium plate with Cu ²⁺ deposited on the surface in step 1 into an argon furnace for heat treatment; the temperature of the heat treatment is 600°C, and the holding time is 2h;

Step 3: Put the porous titanium plate with Cu ²⁺ deposited on the surface heat-treated in step 2 into a nitric acid solution with a mass concentration of 45%, and carry out acid leaching treatment at a temperature of 70 ° C to obtain a nanoporous material; the The nanoporous material is composed of a porous titanium matrix and a needle-shaped nanoporous titanium oxide surface layer.

After testing, the nanoporous material prepared in this example has a bacteriostatic rate of more than 99% against Escherichia coli, and a bacteriostatic rate of more than 99% against Staphylococcus aureus.

Example 2

This embodiment includes the following steps:

Step 1. Use the porous titanium alloy plate prepared by titanium alloy fiber as the cathode, use the platinum sheet as the anode, and use the copper sulfate solution with a mass concentration of 25% as the electrolyte to conduct electrodeposition, so that the Cu ²⁺ in the electrolyte is deposited on the The surface of the porous titanium plate;

Step 2: Put the porous titanium alloy plate with Cu ²⁺ deposited on the surface in Step 1 into an argon furnace for heat treatment; the temperature of the heat treatment is 600°C, and the holding time is 2h;

Step 3: Put the heat-treated porous titanium alloy plate with Cu ²⁺ deposited on the surface into a nitric acid solution with a mass concentration of 45%, and perform an acid leaching treatment at a temperature of 70° C. to obtain a nanoporous material; The nanoporous material is composed of a porous titanium alloy matrix and a needle-shaped nanoporous titanium oxide surface layer.

After testing, the nanoporous material prepared in this example has a bacteriostatic rate of more than 99% against Escherichia coli, and a bacteriostatic rate of more than 99% against Staphylococcus aureus.

Example 3

This embodiment includes the following steps:

Step 1. Use the porous titanium alloy plate prepared from the titanium alloy powder as the cathode, use the graphite as the anode, and use the copper sulfate solution with a mass concentration of 20% as the electrolyte to carry out electrodeposition, so that the Cu ²⁺ in the electrolyte is deposited on the porous surface. the surface of the titanium plate;

Step 2, put the porous titanium plate with Cu ²⁺ deposited on the surface in step 1 into an argon furnace for heat treatment; the temperature of the heat treatment is 500°C, and the holding time is 2h;

Step 3: Put the porous titanium plate with Cu ²⁺ deposited on the surface heat-treated in Step 2 into a nitric acid solution with a mass concentration of 40%, and carry out acid leaching treatment at a temperature of 60° C. to obtain a nanoporous material; the The nanoporous material is composed of a porous titanium alloy matrix and a needle-shaped nanoporous titanium oxide surface layer.

After testing, the nanoporous material prepared in this example has a bacteriostatic rate of more than 99% against Escherichia coli, and a bacteriostatic rate of more than 99% against Staphylococcus aureus.

Example 4

This embodiment includes the following steps:

Step 1. Use the porous titanium plate prepared by titanium fiber as the cathode, use the platinum sheet as the anode, and use the copper sulfate solution with a mass concentration of 10% as the electrolyte to perform electrodeposition, so that the Cu ²⁺ in the electrolyte is deposited on the porous titanium. the surface of the board;

Step 2, put the porous titanium plate with Cu ²⁺ deposited on the surface in step 1 into an argon furnace for heat treatment; the temperature of the heat treatment is 300°C, and the holding time is 1h;

Step 3: Put the heat-treated porous titanium plate with Cu ²⁺ deposited on the surface into a nitric acid solution with a mass concentration of 30%, and perform an acid leaching treatment at a temperature of 30° C. to obtain a nanoporous material; the The nanoporous material is composed of a porous titanium matrix and a needle-shaped nanoporous titanium oxide surface layer.

After testing, the nanoporous material prepared in this example has a bacteriostatic rate of more than 99% against Escherichia coli, and a bacteriostatic rate of more than 99% against Staphylococcus aureus.

Example 5

This embodiment includes the following steps:

Step 1. Use the porous titanium plate prepared by titanium powder as the cathode, use the graphite as the anode, and use the copper sulfate solution with a mass concentration of 30% as the electrolyte to perform electrodeposition, so that the Cu ²⁺ in the electrolyte is deposited on the porous titanium plate. s surface;

Step 2: Put the porous titanium plate with Cu ²⁺ deposited on the surface in step 1 into an argon furnace for heat treatment; the temperature of the heat treatment is 800°C, and the holding time is 5h;

Step 3: Put the heat-treated porous titanium plate with Cu ²⁺ deposited on the surface into a nitric acid solution with a mass concentration of 60%, and perform an acid leaching treatment at a temperature of 70° C. to obtain a nanoporous material; the The nanoporous material is composed of a porous titanium matrix and a needle-shaped nanoporous titanium oxide surface layer.

After testing, the nanoporous material prepared in this example has a bacteriostatic rate of more than 99% against Escherichia coli, and a bacteriostatic rate of more than 99% against Staphylococcus aureus.

The above descriptions are only preferred embodiments of the present invention, and do not limit the present invention in any way. Any simple modifications, changes and equivalent changes made to the above embodiments according to the technical essence of the invention still fall within the protection scope of the technical solutions of the present invention.

Claims (3)

1. a preparation method of antibacterial nanoporous material, is characterized in that, the method comprises the following steps: Step 1. Use porous titanium or porous titanium alloy as the cathode, graphite or platinum sheet as the anode, and copper sulfate solution with a mass concentration of 10% to 30% as the electrolyte to perform electrodeposition, so that the Cu ²⁺ in the electrolyte Deposited on the surface of porous titanium or porous titanium alloys; In step 2, the porous titanium or porous titanium alloy with Cu ²⁺ deposited on the surface in step 1 is put into an argon furnace for heat treatment; the temperature of the heat treatment is 300℃～800℃, and the holding time is 1h～5h; Step 3: Put the heat-treated porous titanium or porous titanium alloy with Cu ²⁺ deposited on the surface into a nitric acid solution for acid leaching to obtain a nanoporous material; the mass concentration of the nitric acid solution is 30% to 60% , the temperature of acid leaching treatment is 30 ℃ ~ 70 ℃. 2 . The method for preparing an antibacterial nanoporous material according to claim 1 , wherein the preparation raw material of the porous titanium in step 1 is titanium powder or titanium fiber, and the preparation raw material of the porous titanium alloy is titanium 2 . Alloy powder or titanium alloy fiber. 3 . The method for preparing an antibacterial nanoporous material according to claim 1 , wherein the nanoporous material obtained in step 3 is composed of a porous titanium or porous titanium alloy matrix and a needle-shaped nanoporous titanium oxide surface layer. 4 .