Preparation method of copper molybdate and titanium dioxide photocatalytic material, product and application

Abstract

The invention relates to a preparation method of a copper molybdate and titanium dioxide photocatalytic material and a product and application of the copper molybdate and titanium dioxide photocatalytic material, the copper molybdate and titanium dioxide photocatalytic material is prepared through a solvothermal method, and molybdenum isopropoxide and organic titanium salt are dissolved in absolute ethyl alcohol for ultrasonic dispersion stirring; dropwise adding deionized water into the turbid liquid to form sol; and adding soluble copper salt into the sol, continuously stirring and adding into a reaction kettle to obtain TiO2 coated with a copper molybdate precursor, washing, drying and calcining to obtain the copper molybdate and titanium dioxide photocatalytic material. The degradation rate of the obtained copper molybdate and titanium dioxide photocatalytic material on tetracycline can reach 99.8%.

Description

Technical Field

[0001] The invention relates to a nanometer photocatalytic material and preparation and application thereof, in particular to a preparation method, product and application of a copper molybdate@titanium dioxide photocatalytic material. Background Art

[0002] By utilizing the properties of semiconductor oxide materials that can be activated under sunlight, organic matter can be effectively oxidized and degraded into small molecules such as carbon dioxide and water. Compared with traditional purification methods, semiconductor photocatalytic technology has the advantages of mild reaction conditions, no secondary pollution, simple operation and obvious degradation effect. Titanium dioxide is one of the most popular photocatalysts, which is low-toxic, low-cost, durable, super-hydrophilic and has excellent photochemical stability.

[0003] Titanium dioxide (TiO2) has attracted much attention as a photocatalytic material. Under light conditions, TiO2 can oxidize organic pollutants in water, making photocatalytic technology a major breakthrough in the treatment of organic pollutants in water and gas phases. Since then, photocatalytic degradation of organic pollutants has gradually become one of the hot fields.

[0004] In order to improve the catalytic efficiency of TiO2 as a photocatalyst, people have used a variety of methods to modify the material. Among them, coating TiO2 not only significantly improves its spectral absorption range, but also promotes the effective separation and transmission of photogenerated charges, thereby improving the photocatalytic performance of the material. Copper molybdate is also an important photocatalyst. The spectral response range of copper molybdate materials is narrow and the efficiency of photogenerated carrier separation is low. Coating it with titanium dioxide further improves the electrochemical performance of the material. Summary of the invention

[0005] In order to overcome the shortcoming that the photocatalytic performance of existing titanium dioxide is not high enough, the purpose of the present invention is to provide a method for preparing a copper molybdate@titanium dioxide photocatalytic material.

[0006] Another object of the present invention is to provide a copper molybdate@titanium dioxide photocatalytic material product obtained by the above method.

[0007] Another object of the present invention is to provide an application of the above product.

[0008] The object of the present invention is achieved by the following scheme: A method for preparing a copper molybdate@titanium dioxide photocatalytic material, preparing the copper molybdate@titanium dioxide photocatalytic material by a solvent thermal method, comprising the following steps: (1) Dissolve molybdenum isopropoxide and organic titanium salt in 70 mL of anhydrous ethanol at a ratio of 100 mmol:1-4 mmol and perform ultrasonic dispersion for 20-30 min, then stir for 1-2 h to obtain a suspension; (2) Add 10 mL of deionized water dropwise into the above suspension to form a sol; (3) Add 100 mmol of soluble copper salt to the above sol, stir continuously for 1-2 h, then add to a 100 mL reactor, react at 160-180 °C for 10-15 h to obtain TiO2 coated with copper molybdate precursor, wash with deionized water 3-5 times, and dry in a vacuum oven at 60-80 °C; (4) Calcine TiO2 coated with copper molybdate precursor at 500-600 °C for 3-5 h to obtain copper molybdate@titanium dioxide photocatalytic material.

[0009] The invention provides a method for preparing a copper molybdate@titanium dioxide photocatalytic material. The invention prepares the copper molybdate@titanium dioxide photocatalytic material by a solvent thermal method. The photocatalytic performance of titanium dioxide can be improved by coating with copper molybdate. The preparation process is relatively simple and easy to operate.

[0010] Preferably, in step (1), the organic titanium salt is one of tetrabutyl titanate, isopropyl titanate or tetraisopropyl titanate, or a combination thereof.

[0011] Preferably, in step (3), the soluble copper salt is one or a combination of copper acetate, copper nitrate or copper chlorate.

[0012] The present invention also provides a copper molybdate@titanium dioxide photocatalytic material, which is prepared according to any of the above methods.

[0013] The present invention also provides an application of copper molybdate@titanium dioxide photocatalytic material to tetracycline degradation in wastewater treatment.

[0014] The advantages of the present invention are: providing a method for preparing copper molybdate@titanium dioxide photocatalytic material by a solvent thermal method, the preparation process is relatively simple and easy to operate. The obtained product can improve the photocatalytic performance of titanium dioxide by coating with copper molybdate. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 This is a diagram of the ultraviolet light catalytic degradation of the copper molybdate@titanium dioxide photocatalytic material of Example 1. DETAILED DESCRIPTION

[0016] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0017] Example 1 A copper molybdate@titanium dioxide photocatalytic material is prepared by a solvothermal method according to the following steps: (1) Dissolve molybdenum isopropoxide and tetrabutyl titanate in 70 mL of anhydrous ethanol at a ratio of 100 mmol:2 mmol, perform ultrasonic dispersion for 30 min, and stir for 2 h to obtain a suspension; (2) Add 10 mL of deionized water dropwise into the above suspension to form a sol; (3) Add 100 mmol of soluble copper acetate to the above sol, stir continuously for 1 h, then add it to a 100 mL reactor and react at 160 °C for 15 h to obtain TiO2 coated with copper molybdate precursor, wash it with deionized water 5 times, and dry it in a vacuum oven at 80 °C; (4) The TiO2 coated with the copper molybdate precursor was calcined at 550 °C for 4 h to obtain the copper molybdate@titanium dioxide photocatalytic material.

[0018] Figure 1 This is the UV-photocatalytic degradation diagram of copper molybdate@titanium dioxide. In the dark, copper molybdate@titanium dioxide first reaches equilibrium in the adsorption of tetracycline, and then under UV-photocatalytic conditions, after 60 minutes, the degradation of tetracycline can reach 99.8%.

[0019] Example 2 A copper molybdate@titanium dioxide photocatalytic material is prepared by a solvothermal method, which is similar to the steps in Example 1 and is prepared according to the following steps: (1) Dissolve molybdenum isopropoxide and ethyl propyl titanate in 70 mL of anhydrous ethanol at a ratio of 100 mmol:2 mmol, perform ultrasonic dispersion for 20 min, and stir for 2 h to obtain a suspension. (2) Add 10 mL of deionized water dropwise into the above suspension to form a sol; (3) Add 100 mmol of soluble copper nitrate to the above sol, stir continuously for 1 h, then add it to a 100 mL reactor and react at 180 °C for 10 h to obtain TiO2 coated with copper molybdate precursor, wash it with deionized water for 3 times, and dry it in a vacuum oven at 60 °C; (4) The TiO2 coated with the copper molybdate precursor was calcined at 500 °C for 5 h to obtain the copper molybdate@titanium dioxide photocatalytic material.

[0020] Example 3 A copper molybdate@titanium dioxide photocatalytic material is prepared by a solvothermal method, which is similar to the steps in Example 1 and is prepared according to the following steps: (1) Dissolve molybdenum isopropoxide and tetrabutyl titanate in 70 mL of anhydrous ethanol at a ratio of 100 mmol:2 mmol, perform ultrasonic dispersion for 30 min, and stir for 2 h to obtain a suspension; (2) Add 10 mL of deionized water dropwise into the above suspension to form a sol; (3) Add 100 mmol of soluble copper chlorate to the above sol, stir continuously for 1 h, then add it to a 100 mL reactor and react at 160 °C for 15 h to obtain TiO2 coated with copper molybdate precursor, wash it with deionized water 5 times, and dry it in a vacuum oven at 80 °C; The TiO2 coated with the copper molybdate precursor was calcined at 600 ℃ for 3 h to obtain the copper molybdate@titanium dioxide photocatalytic material.

Claims

1. A method for preparing a copper molybdate@titanium dioxide photocatalytic material, characterized in that: The method comprises the following steps: preparing copper molybdate@titanium dioxide photocatalytic material by a solvothermal method; (1) Dissolve molybdenum isopropoxide and organic titanium salt in 70 mL of anhydrous ethanol at a ratio of 100 mmol:1-4 mmol, perform ultrasonic dispersion for 20-30 min, and stir for 1-2 h to obtain a suspension; (2) Add 10 mL of deionized water dropwise into the above suspension to form a sol; (3) Add 100 mmol of soluble copper salt to the above sol, stir continuously for 1-2 h, then add to a 100 mL reactor, react at 160-180 °C for 10-15 h to obtain TiO2 coated with copper molybdate precursor, wash with deionized water 3-5 times, and dry in a vacuum oven at 60-80 °C; (4) Calcine TiO2 coated with copper molybdate precursor at 500-600 °C for 3-5 h to obtain copper molybdate@titanium dioxide photocatalytic material.

2. The method for preparing a copper molybdate@titanium dioxide photocatalytic material according to claim 1, characterized in that: The organic titanium salt is one of tetrabutyl titanate, isopropyl titanate and tetraisopropyl titanate or a combination thereof.

3. The copper molybdate@titanium dioxide photocatalytic material according to claim 1, characterized in that The soluble copper salt is one or a combination of copper acetate, copper nitrate or copper chlorate.

4. The copper molybdate@titanium dioxide photocatalytic material according to any one of claims 1 to 3, characterized in that: Prepare as follows: (1) Dissolve molybdenum isopropoxide and tetrabutyl titanate in 70 mL of anhydrous ethanol at a ratio of 100 mmol:2 mmol, perform ultrasonic dispersion for 30 min, and stir for 2 h to obtain a suspension; (2) Add 10 mL of deionized water dropwise into the above suspension to form a sol; (3) Add 100 mmol of soluble copper acetate to the above sol, stir continuously for 1 h, then add it to a 100 mL reactor and react at 160 °C for 15 h to obtain TiO2 coated with copper molybdate precursor, wash it with deionized water 5 times, and dry it in a vacuum oven at 80 °C; (4) The TiO2 coated with the copper molybdate precursor was calcined at 550 °C for 4 h to obtain the copper molybdate@titanium dioxide photocatalytic material.

5. The copper molybdate@titanium dioxide photocatalytic material according to any one of claims 1 to 3, characterized in that: Prepare as follows: (1) Dissolve molybdenum isopropoxide and ethyl propyl titanate in 70 mL of anhydrous ethanol at a ratio of 100 mmol:2 mmol, perform ultrasonic dispersion for 20 min, and stir for 2 h to obtain a suspension. (2) Add 10 mL of deionized water dropwise into the above suspension to form a sol; (3) Add 100 mmol of soluble copper nitrate to the above sol, stir continuously for 1 h, then add it to a 100 mL reactor and react at 180 °C for 10 h to obtain TiO2 coated with copper molybdate precursor, wash it with deionized water for 3 times, and dry it in a vacuum oven at 60 °C; (4) The TiO2 coated with the copper molybdate precursor was calcined at 500 °C for 5 h to obtain the copper molybdate@titanium dioxide photocatalytic material.

6. The copper molybdate@titanium dioxide photocatalytic material according to any one of claims 1 to 3, characterized in that: Prepare as follows: (1) Dissolve molybdenum isopropoxide and tetrabutyl titanate in 70 mL of anhydrous ethanol at a ratio of 100 mmol:2 mmol, perform ultrasonic dispersion for 30 min, and stir for 2 h to obtain a suspension; (2) Add 10 mL of deionized water dropwise into the above suspension to form a sol; (3) Add 100 mmol of soluble copper chlorate to the above sol, stir continuously for 1 h, then add it to a 100 mL reactor and react at 160 °C for 15 h to obtain TiO2 coated with copper molybdate precursor, wash it with deionized water 5 times, and dry it in a vacuum oven at 80 °C; (4) The TiO2 coated with the copper molybdate precursor was calcined at 600 °C for 3 h to obtain the copper molybdate@titanium dioxide photocatalytic material.

7. A copper molybdate@titanium dioxide photocatalytic material, characterized in that Prepared according to any one of claims 1 to 6.

8. Use of the copper molybdate@titanium dioxide photocatalytic material according to claim 7 for degradation of tetracycline in wastewater treatment.

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