Preparation method of titanium dioxide / tungsten trioxide composite material as well as product and application thereof

Abstract

The invention provides a preparation method of a titanium dioxide / tungsten trioxide composite material as well as a product and application thereof, a certain amount of titanium tetrachloride is dropped into ethylene glycol to react for a period of time, a certain amount of copper salt solution is added, and uniform stirring is continued to obtain a solution A; transferring A into a hydrothermal reaction kettle for reaction, washing a product, and drying overnight to obtain B; dispersing the B into the solution, adding a tungstate aqueous solution, adjusting the pH value, stirring, washing and drying to obtain C; the C is placed in a muffle furnace to be calcined, and the titanium dioxide / tungsten trioxide composite material with the large specific surface area is obtained. The loading of tungsten trioxide enhances the absorption of visible light by the material and improves the separation efficiency of electron-hole pairs, and meanwhile, generated carriers have relatively strong oxidation capacity and play a very important role in improving the photocatalytic performance of the material. The degradation rate of the composite material to methylene blue under visible light is about 98%. The preparation process is relatively simple and easy to operate.

Description

Technical Field

[0001] This invention relates to the preparation and application of photocatalytic materials, specifically a method for preparing a titanium dioxide / tungsten trioxide composite material, as well as its products and applications. Background Technology

[0002] With the development of modern technology and the improvement of people's lives, environmental problems such as air and water pollution are becoming increasingly serious. Methylene blue is a common pollutant in dye wastewater, and adopting effective methods to degrade methylene blue is urgently needed to address water pollution. Currently, semiconductor photocatalysts have attracted widespread attention due to their outstanding advantages such as mild reaction conditions, no secondary pollution, and significant degradation effects, and are considered an ideal solution to the environmental pollution problems caused by the discharge of dyeing and printing wastewater. Titanium dioxide, as a semiconductor material with advantages such as good chemical stability, high earth element abundance, resistance to photocorrosion, good thermal stability, and low toxicity, has attracted much attention due to its excellent performance in decomposing pollutants and organic compounds because of its moderate band gap.

[0003] Tungsten trioxide is a typical n-type photocatalyst with advantages such as non-toxicity, excellent resistance to photocorrosion, and high hole oxidation capacity. Many studies have shown that oxidation is a highly effective method for removing pollutants from wastewater. A heterostructure composed of tungsten trioxide and titanium dioxide, due to its suitable band edge positions, can effectively promote carrier separation while generating carriers with strong oxidation capabilities, making it very promising for use in the field of photocatalysis. Summary of the Invention

[0004] In order to overcome the shortcomings of the prior art, the present invention aims to provide a method for preparing titanium dioxide / tungsten trioxide composite materials.

[0005] Another object of the present invention is to provide a product of titanium dioxide / tungsten trioxide nanocomposite material prepared by the above method.

[0006] Another object of the present invention is to provide applications of the above-mentioned products.

[0007] The objective of this invention is achieved through the following method: a method for preparing titanium dioxide / tungsten trioxide nanocomposite materials, comprising the following steps: 1. A certain amount of titanium tetrachloride is added dropwise to ethylene glycol and reacted for a period of time. Then, a certain amount of copper salt solution is added, wherein the mass ratio of copper to titanium tetrachloride is 1:20. The mixture is then stirred magnetically for 1-2 hours until it is uniformly mixed, thus obtaining solution A. 2. Transfer A to a hydrothermal reactor, heat to 140-160 °C and react for 4-5 h, cool to room temperature, wash the reaction product 3-5 times with deionized water and organic solvent, and dry in an oven at 60-80 °C overnight to obtain precursor B; 3. Disperse precursor B in a solution, add an aqueous solution of tungstate of a certain concentration, adjust the pH to 1-3 with hydrochloric acid, continue magnetic stirring for 2-4 h, wash the reaction product with deionized water and organic solvent 3-5 times, and dry it overnight in an oven at 60-80℃ to obtain precursor C; 4. Place the precursor C in a muffle furnace and calcine it to 300-400℃ at a heating rate of 2-5℃ / min, and hold it at that temperature for 4-6 hours to obtain a titanium dioxide / tungsten trioxide composite material.

[0008] This invention provides a method for preparing titanium dioxide / tungsten trioxide nanocomposite photocatalytic materials. The preparation process is relatively simple and easy to operate.

[0009] The copper salt is one or a combination of copper sulfate and copper nitrate; the tungstate is one or a combination of sodium tungstate and potassium tungstate.

[0010] The organic solvent is one of ethanol, acetone, or a combination thereof.

[0011] This invention provides a titanium dioxide / tungsten trioxide nanocomposite material, prepared according to any of the methods described above.

[0012] This invention provides an application of titanium dioxide / tungsten trioxide composite material as a photocatalytic material in wastewater treatment.

[0013] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention provides a method for preparing a titanium dioxide / tungsten trioxide nanocomposite photocatalytic material. The process is relatively simple and easy to operate. The titanium dioxide / tungsten trioxide nanocomposite photocatalytic material has a large specific surface area. The loading of tungsten trioxide enhances the absorption of visible light and improves the electron-hole pair separation efficiency. Simultaneously, the generated charge carriers possess strong oxidizing ability, playing a crucial role in improving the photocatalytic performance of the material. The preparation process is relatively simple and easy to operate. The composite material exhibits a degradation rate of approximately 98% for methylene blue under visible light. Attached Figure Description

[0014] Figure 1 The image shows the visible light catalytic degradation rate of the prepared titanium dioxide / tungsten trioxide composite material. Detailed Implementation

[0015] The present invention will be described in detail through the following specific examples, but the scope of protection of the present invention is not limited to these embodiments.

[0016] Example 1 A titanium dioxide / tungsten trioxide composite material is prepared according to the following steps: 1) After adding titanium tetrachloride dropwise into ethylene glycol and reacting for a period of time, a certain amount of copper sulfate solution is added, wherein the mass ratio of copper to titanium tetrachloride is 1:20; continue magnetic stirring for 2 hours until the solution is uniformly mixed to obtain solution A; 2) Transfer solution A to a hydrothermal reactor, heat to 160 °C and react for 4 h, cool to room temperature, wash the reaction product three times with deionized water and organic solvent, and dry it overnight at 60 °C in an oven to obtain precursor B; 3) Disperse precursor B into a solution, add an aqueous solution of tungstate of a certain concentration, adjust the pH to 2 with hydrochloric acid, continue magnetic stirring for 2 h, wash the reaction product three times with deionized water and organic solvent, and dry it overnight in an oven at 60 ℃ to obtain precursor C; 4) Place the precursor C in a muffle furnace and calcine it to 350°C at a heating rate of 2°C / min, and hold it at that temperature for 4 hours to obtain a titanium dioxide / tungsten trioxide composite material.

[0017] The visible light photocatalytic degradation rate of the prepared titanium dioxide / tungsten trioxide composite material is shown in the figure. Figure 1 As shown, the composite material exhibits a degradation rate of approximately 98% for methylene blue under visible light. The preparation process is relatively simple and easy to operate.

[0018] Example 2 A titanium dioxide / tungsten trioxide composite material is prepared according to the following steps: 1) Titanium tetrachloride was added dropwise to ethylene glycol and reacted for a period of time. Then, copper sulfate solution was added, wherein the mass ratio of copper to titanium tetrachloride was 1:20. The mixture was stirred magnetically for 2 hours until it was uniformly mixed, and solution A was obtained. 2) Transfer solution A to a hydrothermal reactor, heat to 150 °C and react for 5 h, cool to room temperature, wash the reaction product 3-5 times with deionized water and organic solvent, and dry in an oven at 60 °C overnight to obtain precursor B; 3) Disperse precursor B into a solution, add an aqueous solution of tungstate of a certain concentration, adjust the pH to 2 with hydrochloric acid, continue magnetic stirring for 2 h, wash the reaction product 5 times with deionized water and organic solvent, and dry it overnight in an oven at 60 ℃ to obtain precursor C; 4) Place the precursor C in a muffle furnace and calcine it to 400℃ at a heating rate of 5℃ / min, and hold it at that temperature for 3 h to obtain a titanium dioxide / tungsten trioxide composite material.

[0019] Example 3 A titanium dioxide / tungsten trioxide composite material is prepared according to the following steps: 1) After adding titanium tetrachloride dropwise into ethylene glycol and reacting for a period of time, copper nitrate solution is added, wherein the mass ratio of copper to titanium tetrachloride is 1:20; magnetic stirring is continued for 2 hours until the solution is uniformly mixed to obtain solution A; 2) Transfer solution A to a hydrothermal reactor, heat to 160 °C and react for 5 h, cool to room temperature, wash the reaction product three times with deionized water and acetone, and dry in an oven at 80 °C overnight to obtain precursor B; 3) Disperse precursor B into a solution, add an aqueous solution of tungstate of a certain concentration, adjust the pH to 1 with hydrochloric acid, continue magnetic stirring for 2 h, wash the reaction product 5 times with deionized water and organic solvent acetone, and dry it overnight in an oven at 80 ℃ to obtain precursor C. 4) Place the precursor C in a muffle furnace and calcine it to 300℃ at a heating rate of 5℃ / min, and hold it at that temperature for 6 h to obtain a titanium dioxide / tungsten trioxide composite material.

Claims

1. A method for preparing a titanium dioxide / tungsten trioxide composite material, characterized in that, Includes the following steps, 1) After reacting titanium tetrachloride dropwise into ethylene glycol for a period of time, add copper salt solution, with the mass ratio of copper to titanium tetrachloride being 1:20; continue magnetic stirring for 1-2 h until the solution is uniformly mixed to obtain solution A; 2) Transfer A to a hydrothermal reactor, heat to 140-160 ℃ and react for 4-5 h, cool to room temperature, wash the reaction product 3-5 times with deionized water and organic solvent, and dry in an oven at 60-80 ℃ overnight to obtain precursor B; 3) Disperse precursor B into a solution, add an aqueous solution of tungstate of a certain concentration, adjust the pH to 1-3 with hydrochloric acid, continue magnetic stirring for 2-4 h, wash the reaction product with deionized water and organic solvent 3-5 times, and dry it overnight in an oven at 60-80 ℃ to obtain precursor C; 4) Place the precursor C in a muffle furnace and calcine it to 300-400℃ at a heating rate of 2-5℃ / min, and hold it for 3-6 h to obtain the titanium dioxide / tungsten trioxide composite material.

2. The method for preparing a titanium dioxide / tungsten trioxide composite material according to claim 1, characterized in that... In step 1), the copper salt is one or a combination of copper sulfate and copper nitrate; the tungstate is one or a combination of sodium tungstate and potassium tungstate.

3. The method for preparing a titanium dioxide / tungsten trioxide composite material according to claim 1, characterized in that... In step 2), the organic solvent is one of ethanol, acetone, or a combination thereof.

4. A method for preparing a titanium dioxide / tungsten trioxide composite material according to any one of claims 1 to 3, characterized in that, Prepare according to the following steps: 1) After adding titanium tetrachloride dropwise into ethylene glycol and reacting for a period of time, a certain amount of copper sulfate solution is added, wherein the mass ratio of copper to titanium tetrachloride is 1:20; continue magnetic stirring for 2 hours until the solution is uniformly mixed to obtain solution A; 2) Transfer solution A to a hydrothermal reactor, heat to 160 °C and react for 4 h, cool to room temperature, wash the reaction product three times with deionized water and organic solvent, and dry it overnight at 60 °C in an oven to obtain precursor B; 3) Disperse precursor B into a solution, add an aqueous solution of tungstate of a certain concentration, adjust the pH to 2 with hydrochloric acid, continue magnetic stirring for 2 h, wash the reaction product three times with deionized water and organic solvent, and dry it overnight in an oven at 60 ℃ to obtain precursor C; 4) Place the precursor C in a muffle furnace and calcine it to 350℃ at a heating rate of 2℃ / min, and hold it at that temperature for 4 hours to obtain a titanium dioxide / tungsten trioxide composite material.

5. A method for preparing a titanium dioxide / tungsten trioxide composite material according to any one of claims 1 to 3, characterized in that, Prepare according to the following steps: 1) Titanium tetrachloride was added dropwise to ethylene glycol and reacted for a period of time. Then, copper sulfate solution was added, wherein the mass ratio of copper to titanium tetrachloride was 1:

20. The mixture was stirred magnetically for 2 hours until it was uniformly mixed, and solution A was obtained. 2) Transfer solution A to a hydrothermal reactor, heat to 150 °C and react for 5 h, cool to room temperature, wash the reaction product 3-5 times with deionized water and organic solvent, and dry in an oven at 60 °C overnight to obtain precursor B; 3) Disperse precursor B into a solution, add an aqueous solution of tungstate of a certain concentration, adjust the pH to 2 with hydrochloric acid, continue magnetic stirring for 2 h, wash the reaction product 5 times with deionized water and organic solvent, and dry it overnight in an oven at 60 ℃ to obtain precursor C; 4) Place the precursor C in a muffle furnace and calcine it to 400℃ at a heating rate of 5℃ / min, and hold it at that temperature for 3 h to obtain a titanium dioxide / tungsten trioxide composite material.

6. A method for preparing a titanium dioxide / tungsten trioxide composite material according to any one of claims 1 to 3, characterized in that, Prepare according to the following steps: 1) After adding titanium tetrachloride dropwise into ethylene glycol and reacting for a period of time, copper nitrate solution is added, wherein the mass ratio of copper to titanium tetrachloride is 1:20; magnetic stirring is continued for 2 hours until the solution is uniformly mixed to obtain solution A; 2) Transfer solution A to a hydrothermal reactor, heat to 160 °C and react for 5 h, cool to room temperature, wash the reaction product three times with deionized water and acetone, and dry in an oven at 80 °C overnight to obtain precursor B; 3) Disperse precursor B into a solution, add an aqueous solution of tungstate of a certain concentration, adjust the pH to 1 with hydrochloric acid, continue magnetic stirring for 2 h, wash the reaction product 5 times with deionized water and organic solvent acetone, and dry it overnight in an oven at 80 ℃ to obtain precursor C. 4) Place the precursor C in a muffle furnace and calcine it to 300℃ at a heating rate of 5℃ / min, and hold it at that temperature for 6 h to obtain a titanium dioxide / tungsten trioxide composite material.

7. A titanium dioxide / tungsten trioxide composite material, prepared by the method according to any one of claims 1-6.

8. The application of the titanium dioxide / tungsten trioxide composite material according to claim 7 as a photocatalytic material in wastewater treatment.

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