Preparation of copper-loaded oxygen-deficient silver molybdate photocatalytic material as well as product and application of copper-loaded oxygen-deficient silver molybdate photocatalytic material
The copper-supported oxygen-deficient silver molybdate photocatalytic material was prepared by the method of surfactant-free and mild chemical solution, which solved the problem of low catalytic efficiency of existing silver molybdate photocatalytic materials and achieved efficient photocatalytic degradation.
Patent Information
- Application Number
- CN202411771597.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-04
- Publication Date
- 2025-02-25
AI Technical Summary
The catalytic efficiency of existing silver molybdate photocatalytic materials is not high enough, especially in the ultraviolet light region, the catalytic performance is limited.
Copper-supported oxygen-deficient silver molybdate photocatalytic material was prepared by surfactant-free and gentle chemical solution method, and nanowire structure was adopted to improve its spectral absorption range and separation and transport ability of photogenerated charges.
The photocatalytic performance of the material has been significantly improved, so that it can effectively degrade methyl orange under ultraviolet photocatalytic conditions, with a degradation rate of 99.6%.
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Abstract
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-loaded oxygen-deficient silver molybdate photocatalytic material. Background Art
[0002] With the development of the chemical industry, the discharge of printing and dyeing wastewater is one of the important causes of water pollution. Every year, a large amount of commercial dyes are discharged. These dyes have stable chemical properties and cause great harm to the ecological environment. By utilizing the characteristics 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. Common traditional photocatalysts are materials such as titanium dioxide and zinc oxide with large bandgap width, which also have good photocatalytic properties. Of course, these materials have better catalytic properties in the ultraviolet light region, and there are certain limitations in real life.
[0003] Silver molybdate itself has certain antibacterial properties and can also be used as a new type of photocatalytic material. Under light conditions, it can not only sterilize sewage, but also treat organic pollutants in the water phase through photocatalytic technology.
[0004] In order to improve the catalytic efficiency of silver molybdate as a photocatalyst, people have used a variety of methods to modify the material. Among them, loading silver molybdate with copper 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. In addition, oxygen defects can further improve the photocatalytic performance of silver molybdate.
[0005] The present invention provides a method for preparing a copper-loaded oxygen-deficient silver molybdate photocatalytic material. The present invention prepares the copper-loaded oxygen-deficient silver molybdate photocatalytic material by a surfactant-free and mild chemical solution method. The prepared material is a nanowire structure with a large specific surface area. Not only is its spectral absorption range significantly improved, but it also promotes the effective separation and transmission of photogenerated charges, thereby improving the photocatalytic performance of the material; the preparation process is relatively simple and easy to operate. Summary of the invention
[0006] In order to overcome the shortcoming that the existing silver molybdate photocatalytic performance is not high enough, the purpose of the present invention is to provide a method for preparing a copper-loaded oxygen-deficient silver molybdate photocatalytic material.
[0007] Another object of the present invention is to provide a copper-loaded oxygen-deficient silver molybdate product obtained by the above method.
[0008] Another object of the present invention is to provide an application of the above product.
[0009] The object of the present invention is achieved by the following scheme: A method for preparing a copper-loaded oxygen-deficient silver molybdate photocatalytic material, characterized in that the copper-loaded oxygen-deficient silver molybdate photocatalytic material is prepared by a surfactant-free and mild chemical solution method, comprising the following steps: (1) 4-8 mL of acetylacetone solution and 8-16 mL of hydrazine hydrate were added sequentially into a flask containing a dispersed phase of a molybdenum source and a silver source, wherein the molar ratio of molybdenum to silver was 1:2. The mixed solution was magnetically stirred and refluxed at 70-90 °C for 36-48 h to obtain A. (2) Filter A, wash with deionized water 2-3 times, and then dry in an oven at 60-80 °C to obtain precursor powder B; (3) calcining B at 400-500 °C for 1-2 h at a heating rate of 0.5-1 °C / min in a hydrogen atmosphere to obtain oxygen-deficient silver molybdate, denoted as C; (4) Disperse C in deionized water and stir evenly, then slowly add 0.5-1 mmol copper salt solution to the solution and stir magnetically for 1-2 h to obtain D. (5) Slowly add D into 1 M ascorbic acid, soak for 60-90 min, centrifuge, and dry in a vacuum oven at 60-80 °C for 6-10 h to obtain copper-loaded oxygen-deficient silver molybdate.
[0010] Preferably, in step (1), the molybdenum source is one or a combination of ammonium molybdate, potassium molybdate or sodium molybdate.
[0011] Preferably, in step (1), the silver source is silver nitrate or silver chlorate or a combination thereof.
[0012] Preferably, the copper salt in step (4) is one or a combination of copper nitrate, copper acetate or copper citrate.
[0013] The present invention also provides a copper-loaded oxygen-deficient silver molybdate photocatalytic material, which is prepared according to any of the above methods.
[0014] The present invention also provides an application of a copper-loaded oxygen-deficient silver molybdate photocatalytic material in wastewater treatment.
[0015] The present invention prepares copper-loaded oxygen-deficient silver molybdate photocatalytic material by a surfactant-free and mild chemical solution method. The prepared material is a nanowire structure with a large specific surface area. Not only is its spectral absorption range significantly improved, but it also promotes the effective separation and transmission of photogenerated charges, thereby improving the photocatalytic performance of the material; the preparation process is relatively simple and easy to operate.
[0016] The copper-loaded oxygen-deficient silver molybdate photocatalytic material first reached equilibrium in the adsorption of methyl orange in the dark, and then under ultraviolet photocatalytic conditions, the degradation of methyl orange reached 99.6% after 60 minutes. BRIEF DESCRIPTION OF THE DRAWINGS
[0017] Figure 1 This is a diagram of the ultraviolet photocatalytic degradation of copper-loaded oxygen-deficient silver molybdate of Example 1.
[0018] The copper-loaded oxygen-deficient silver molybdate photocatalytic material first reached equilibrium in the adsorption of methyl orange in the dark, and then under ultraviolet photocatalytic conditions, the degradation of methyl orange reached 99.6% after 60 minutes. DETAILED DESCRIPTION
[0019] 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.
[0020] Example 1 A copper-loaded oxygen-deficient silver molybdate photocatalytic material is prepared by a surfactant-free and mild chemical solution method, and is prepared according to the following steps: (1) 8 mL of acetylacetone solution and 16 mL of hydrazine hydrate were added sequentially into a flask containing ammonium molybdate and silver nitrate dispersed phases, wherein the molar ratio of molybdenum to silver was 1:2. The mixed solution was magnetically stirred and refluxed at 90 °C for 48 h to obtain A. (2) Filter A, wash it with deionized water three times, and dry it in an oven at 80 °C to obtain precursor powder B; (3) calcining B at 500 °C for 1 h at a heating rate of 1 °C / min in a hydrogen atmosphere to obtain oxygen-deficient silver molybdate, denoted as C; (4) Disperse C in deionized water and stir evenly, then slowly add 1 mmol of copper nitrate to the solution and stir magnetically for 2 h to obtain D. (5) D was slowly added to 1 M ascorbic acid, immersed for 90 min, centrifuged, and dried in a vacuum oven at 80 °C for 6 h to obtain copper-loaded oxygen-deficient silver molybdate.
[0021] Figure 1This is a diagram of the ultraviolet photocatalytic degradation of copper-loaded oxygen-deficient silver molybdate photocatalyst. The copper-loaded oxygen-deficient silver molybdate photocatalyst first reaches equilibrium in the adsorption of methyl orange in the dark, and then under ultraviolet photocatalytic conditions, after 60 minutes, the degradation of methyl orange reaches 99.6%.
[0022] Example 2 A copper-loaded oxygen-deficient silver molybdate photocatalytic material is prepared similarly to Example 1 by the following steps: (1) 4 mL of acetylacetone solution and 8 mL of hydrazine hydrate were added sequentially into a flask containing potassium molybdate and silver nitrate dispersed phases, wherein the molar ratio of molybdenum to silver was 1:2. The mixed solution was magnetically stirred and refluxed at 70 °C for 36 h to obtain A. (2) Filter A, wash it with deionized water three times, and dry it in an oven at 60 °C to obtain precursor powder B; (3) calcining B at 400 °C for 2 h at a heating rate of 1 °C / min in a hydrogen atmosphere to obtain oxygen-deficient silver molybdate, denoted as C; (4) Disperse C in deionized water and stir evenly, then slowly add 1 mmol of copper acetate to the solution and stir magnetically for 2 h to obtain D. (5) D was slowly added to 1 M ascorbic acid, immersed for 90 min, centrifuged, and dried in a vacuum oven at 80 °C for 6 h to obtain copper-loaded oxygen-deficient silver molybdate.
[0023] Example 3 A copper-loaded oxygen-deficient silver molybdate photocatalytic material is prepared similarly to Example 1 by the following steps: (1) 6 mL of acetylacetone solution and 12 mL of hydrazine hydrate were added sequentially into a flask containing sodium molybdate and silver chlorate dispersed phases, wherein the molar ratio of molybdenum to silver was 1:2. The mixed solution was magnetically stirred and refluxed at 90 °C for 48 h to obtain A. (2) Filter A, wash it with deionized water three times, and dry it in an oven at 80 °C to obtain precursor powder B; (3) calcining B at 500 °C for 1 h at a heating rate of 1 °C / min in a hydrogen atmosphere to obtain oxygen-deficient silver molybdate, denoted as C; (4) Disperse C in deionized water and stir evenly, then slowly add 1 mmol of copper citrate to the solution and stir magnetically for 2 h to obtain D. (5) D was slowly added to 1 M ascorbic acid, immersed for 70 min, centrifuged, and dried in a vacuum oven at 80 °C for 6 h to obtain copper-loaded oxygen-deficient silver molybdate.
Claims
1. A method for preparing a copper-loaded oxygen-deficient silver molybdate photocatalytic material, characterized in that: The copper-supported oxygen-deficient silver molybdate photocatalytic material is prepared by a surfactant-free and mild chemical solution method, comprising the following steps: (1) 4-8 mL of acetylacetone solution and 8-16 mL of hydrazine hydrate were added sequentially into a flask containing a dispersed phase of a molybdenum source and a silver source, wherein the molar ratio of molybdenum to silver was 1:
2. The mixed solution was magnetically stirred and refluxed at 70-90 °C for 36-48 h to obtain A; (2) Filter A, wash it with deionized water 2 to 3 times, and dry it in an oven at 60 to 80 °C to obtain precursor powder B; (3) calcining the precursor powder B at 400-500 °C for 1-2 h at a heating rate of 0.5-1 °C / min in a hydrogen atmosphere to obtain oxygen-deficient silver molybdate, denoted as C; (4) Disperse C in deionized water and stir evenly, then slowly add 0.5-1 mmol copper salt solution to the solution and stir magnetically for 1-2 h to obtain D. (5) D was slowly added to 1 M ascorbic acid, immersed for 60-90 min, centrifuged, and dried in a vacuum oven at 60-80 °C for 6-10 h to obtain copper-loaded oxygen-deficient silver molybdate.
2. The method for preparing a copper-loaded oxygen-deficient silver molybdate photocatalytic material according to claim 1, characterized in that The molybdenum source is one of ammonium molybdate, potassium molybdate and sodium molybdate or a combination thereof.
3. The method for preparing a copper-loaded oxygen-deficient silver molybdate photocatalytic material according to claim 1, characterized in that The silver source is silver nitrate or silver chlorate or a combination thereof.
4. The method for preparing a copper-loaded oxygen-deficient silver molybdate photocatalytic material according to claim 1, characterized in that The copper salt is one of copper nitrate, copper acetate or copper citrate or a combination thereof.
5. The method for preparing a copper-loaded oxygen-deficient silver molybdate photocatalytic material according to any one of claims 1 to 4, characterized in that: Prepare as follows: (1) 8 mL of acetylacetone solution and 16 mL of hydrazine hydrate were added sequentially into a flask containing ammonium molybdate and silver nitrate dispersed phases, wherein the molar ratio of molybdenum to silver was 1:
2. The mixed solution was magnetically stirred and refluxed at 90 °C for 48 h to obtain A. (2) Filter A, wash it with deionized water three times, and dry it in an oven at 80 °C to obtain precursor powder B; (3) calcining B at 500 °C for 1 h at a heating rate of 1 °C / min in a hydrogen atmosphere to obtain oxygen-deficient silver molybdate, denoted as C; (4) Disperse C in deionized water and stir evenly, then slowly add 1 mmol of copper nitrate to the solution and stir magnetically for 2 h to obtain D. (5) D was slowly added to 1 M ascorbic acid, immersed for 90 min, centrifuged, and dried in a vacuum oven at 80 °C for 6 h to obtain copper-loaded oxygen-deficient silver molybdate.
6. The method for preparing a copper-loaded oxygen-deficient silver molybdate photocatalytic material according to any one of claims 1 to 4, characterized in that: The preparation was carried out as follows: (1) 4 mL of acetylacetone solution and 8 mL of hydrazine hydrate were added sequentially into a flask containing potassium molybdate and silver nitrate dispersed phases, wherein the molar ratio of molybdenum to silver was 1:2, and the mixed solution was magnetically stirred and refluxed at 70 °C for 36 h to obtain A; (2) Filter A, wash it with deionized water three times, and dry it in an oven at 60 °C to obtain precursor powder B; (3) calcining B at 400 °C for 2 h at a heating rate of 1 °C / min in a hydrogen atmosphere to obtain oxygen-deficient silver molybdate, denoted as C; (4) Disperse C in deionized water and stir evenly, then slowly add 1 mmol of copper acetate to the solution and stir magnetically for 2 h to obtain D. (5) D was slowly added to 1 M ascorbic acid, immersed for 90 min, centrifuged, and dried in a vacuum oven at 80 °C for 6 h to obtain copper-loaded oxygen-deficient silver molybdate.
7. The method for preparing a copper-loaded oxygen-deficient silver molybdate photocatalytic material according to any one of claims 1 to 4, characterized in that: The preparation was carried out as follows: (1) 6 mL of acetylacetone solution and 12 mL of hydrazine hydrate were added sequentially into a flask containing sodium molybdate and silver chlorate dispersed phases, wherein the molar ratio of molybdenum to silver was 1:2, and the mixed solution was magnetically stirred and refluxed at 90 °C for 48 h to obtain A; (2) Filter A, wash it with deionized water three times, and dry it in an oven at 80 °C to obtain precursor powder B; (3) calcining B at 500 °C for 1 h at a heating rate of 1 °C / min in a hydrogen atmosphere to obtain oxygen-deficient silver molybdate, denoted as C; (4) Disperse C in deionized water and stir evenly, then slowly add 1 mmol of copper citrate to the solution and stir magnetically for 2 h to obtain D. (5) D was slowly added to 1 M ascorbic acid, immersed for 70 min, centrifuged, and dried in a vacuum oven at 80 °C for 6 h to obtain copper-loaded oxygen-deficient silver molybdate.
8. A copper-loaded oxygen-deficient silver molybdate photocatalytic material, characterized in that Prepared according to any one of claims 1 to 7.
9. Use of the copper-loaded oxygen-deficient silver molybdate photocatalytic material according to claim 8 for degrading methyl orange in wastewater treatment.