Preparation method, product and application of zinc oxide / silver molybdate nanophotocatalytic material

Abstract

The present invention provides a preparation method, product and application of a zinc oxide / silver molybdate nanophotocatalytic material. The method includes: fully mixing a molybdenum source, silver oxide and a zinc salt according to a stoichiometric molar ratio and grinding them in a mortar to obtain A; transferring the obtained mixture to a 20-milliliter glass vial, adding another 3-milliliter open vial containing 1 milliliter of distilled water therein; then, after reacting the whole container in an oven at 70-80 °C for 24-30 h, taking out the water vial, drying it at the same temperature for 12-18 h and then re-grinding to obtain B; placing B in a muffle furnace and calcining it at a heating rate of 1-2 °C / min to 350-500 °C for 2-4 h to obtain the final product, i.e., the zinc oxide / silver molybdate nanophotocatalytic material. After the adsorption of methyl orange reaches equilibrium in the dark first, under the condition of ultraviolet photocatalysis, after 60 min, the degradation of methyl orange reaches 99.6%.

Description

Technical Field

[0001] The present invention relates to nano-photocatalytic materials and their preparation and applications, specifically to a preparation method, product and application of zinc oxide / silver molybdate nano-photocatalytic materials. Background Art

[0002] The discharge of printing and dyeing wastewater is one of the important causes of water pollution. A large amount of commercial dyes are discharged every year. These dyes have stable chemical properties and cause great harm to the ecological environment. Utilizing the property that semiconductor materials can be activated under sunlight irradiation, organic matter can be effectively oxidized and degraded into small molecules such as carbon dioxide and water.

[0003] As an important semiconductor photocatalyst in the molybdate family, silver molybdate has good photocatalytic activity. However, silver molybdate materials have a narrow spectral response range, low separation efficiency of photo-generated carriers, and low photocatalytic efficiency in the visible light region. For this reason, in response to this problem, researchers have prepared composites based on silver molybdate to expand its optical absorption range, promote the separation of photo-generated carriers, and thus greatly improve its photocatalytic performance in the visible light region.

[0004] As a photocatalyst, nano-zinc oxide particles can increase the reaction rate by 100 - 1000 times, do not cause light scattering, and have a large specific surface area and a wide energy band. Nano-zinc oxide, as an active substance, can be used in various catalytic reactions and is considered to be one of the highly promising highly active photocatalysts. Combining zinc oxide with silver molybdate can improve the photocatalytic performance of silver molybdate materials to a certain extent.

[0005] The present invention provides a preparation method of zinc oxide / silver molybdate nano-photocatalytic materials. The present invention prepares zinc oxide / silver molybdate nano-photocatalytic materials by a special solid-phase method, namely a wet-assisted solid-phase method. Humidity plays a key role in the reaction of the solid-phase method and can ultimately control the size and morphology of the materials, thereby improving the photocatalytic performance of the composite materials. This preparation process is relatively simple and easy to operate. Summary of the Invention

[0006] To overcome the deficiency of the insufficient photocatalytic performance of existing titanium dioxide, the object of the present invention is to provide a preparation method of zinc oxide / silver molybdate nano-photocatalytic materials.

[0007] Another object of the present invention is to provide a product of zinc oxide / silver molybdate nano-photocatalytic materials 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 zinc oxide / silver molybdate nano-photocatalytic material, characterized in that the zinc oxide / silver molybdate nano-photocatalytic material is prepared by a special solid-phase method, namely a wet-assisted solid-phase method, and the specific steps of the method are:

[0010] (1) Molybdenum source, silver oxide, and zinc salt are thoroughly mixed in a stoichiometric molar ratio (1:2:0.1-0.3) and ground in a mortar to obtain A;

[0011] (2) The obtained mixture was transferred to a 20 ml glass vial, into which another 3 ml open vial containing 1 ml of distilled water was added. Then, the entire container was kept in an oven at 70-80 °C. After reacting for 24-30 h, the vial was taken out, dried at the same temperature for 12-18 h, and then ground again to obtain B;

[0012] (3) Place B in a muffle furnace and heat it to 350-500°C at a heating rate of 1-2°C / min and calcine it for 2-4 h to obtain the final product, zinc oxide / silver molybdate nanophotocatalytic material.

[0013] Preferably, in step (1), the molybdenum source is one of ammonium molybdate and molybdenum trioxide, or a combination thereof.

[0014] Preferably, in step (1), the zinc salt is one of zinc acetate, zinc formate or zinc gluconate or a combination thereof.

[0015] The present invention provides a zinc oxide / silver molybdate nanometer photocatalytic material, which is prepared according to any of the above methods.

[0016] The present invention provides an application of a zinc oxide / silver molybdate nanometer photocatalytic material in the degradation treatment of methyl orange in dye wastewater.

[0017] The present invention has the beneficial effects of preparing a zinc oxide / silver molybdate nanophotocatalytic material via a unique solid-phase method, namely a wet-assisted solid-phase method. Humidity plays a key role in the reaction in the solid-phase method and can ultimately control the size and morphology of the material, thereby improving the photocatalytic performance of the composite material. The preparation process is relatively simple and easy to operate. After the zinc oxide / silver molybdate nanophotocatalytic material first reaches equilibrium adsorption of methyl orange in the dark, it degrades methyl orange by 99.6% under ultraviolet light after 60 minutes. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 This is a diagram of the ultraviolet photocatalytic degradation of the zinc oxide / silver molybdate nanophotocatalytic material in Example 1. DETAILED DESCRIPTION

[0019] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts belong to the scope of protection of the present invention.

[0020] Example 1

[0021] A zinc oxide / silver molybdate nanophotocatalytic material is prepared by a wet-assisted solid-phase method to prepare the zinc oxide / silver molybdate nanophotocatalytic material, and is prepared according to the following steps:

[0022] (1) Ammonium molybdate, silver oxide, and zinc acetate are fully mixed according to a stoichiometric molar ratio of 1:2:0.1 and ground in a mortar to obtain mixture A;

[0023] (2) Transfer the obtained mixture A to a 20-ml glass vial, and add another 3-ml open vial containing 1 ml of distilled water; then, the entire container is reacted in an oven at 80 °C for 24 h, the small water bottle is taken out, dried at the same temperature for 12 h, and then re-ground to obtain powder B;

[0024] (3) Place powder B in a muffle furnace and heat it to 350 °C at a heating rate of 1 °C / min for calcination for 4 h to obtain the final product zinc oxide / silver molybdate nanophotocatalytic material.

[0025] Figure 1 It is the ultraviolet photocatalytic degradation diagram of the zinc oxide / silver molybdate nanophotocatalytic material. The zinc oxide / silver molybdate nanophotocatalytic material first adsorbs methyl orange to equilibrium in the dark, and then under ultraviolet photocatalytic conditions, after 60 min, the degradation of methyl orange reaches 99.6%.

[0026] Example 2

[0027] A zinc oxide / silver molybdate nanophotocatalytic material, similar to Example 1, is prepared according to the following steps:

[0028] (1) Molybdenum trioxide, silver oxide, and zinc formate are fully mixed according to a stoichiometric molar ratio of 1:2:0.2 and ground in a mortar to obtain mixture A;

[0029] (2) Transfer the obtained mixture A to a 20-ml glass vial, and add another 3-ml open vial containing 1 ml of distilled water; the entire container is reacted in an oven at 70 °C for 30 h, the small water bottle is taken out, dried at the same temperature for 18 h, and then re-ground to obtain powder B;

[0030] (3) Powder B was placed in a muffle furnace and heated to 400°C at a heating rate of 2°C / min for calcination for 3 h to obtain the final product, zinc oxide / silver molybdate nanophotocatalytic material.

[0031] Example 3

[0032] A zinc oxide / silver molybdate nano-photocatalytic material was prepared similarly to that in Example 1 by the following steps:

[0033] (1) Ammonium molybdate, silver oxide, and zinc gluconate were thoroughly mixed in a stoichiometric molar ratio of 1:2:0.3 and ground in a mortar to obtain a mixture A;

[0034] (2) The obtained mixture A was transferred to a 20 ml glass vial, into which another 3 ml open vial containing 1 ml of distilled water was added; after the entire container was reacted in an oven at 80 °C for 30 h, the vial was taken out, dried at the same temperature for 12 h, and then re-ground to obtain powder B;

[0035] (3) Powder B was placed in a muffle furnace and heated to 500°C at a heating rate of 2°C / min for calcination for 2 h to obtain the final product, zinc oxide / silver molybdate nanophotocatalytic material.

Claims

1. A method for preparing a zinc oxide / silver molybdate nano-photocatalytic material, characterized in that: The method comprises the following steps: preparing a zinc oxide / silver molybdate nano-photocatalytic material by a wet-assisted solid phase method; (1) Molybdenum source, silver oxide, and zinc salt were thoroughly mixed in a stoichiometric molar ratio of 1:2:(0.1-0.3) and ground in a mortar to obtain a mixture A; (2) The obtained mixture A was transferred to a 20 ml glass vial, into which another 3 ml open vial containing 1 ml of distilled water was added; after the entire container was reacted in an oven at 70-80 °C for 24-30 h, the vial was removed and dried at the same temperature for 12-18 h, and then ground again to obtain powder B; (3) Powder B was placed in a muffle furnace and heated to 350-500°C at a heating rate of 1-2°C / min and calcined for 2-4 h to obtain the final product, zinc oxide / silver molybdate nano-photocatalytic material.

2. The method for preparing the zinc oxide / silver molybdate nano-photocatalytic material according to claim 1, characterized in that: The molybdenum source is one of ammonium molybdate and molybdenum trioxide or a combination thereof.

3. The method for preparing the zinc oxide / silver molybdate nano-photocatalytic material according to claim 1, characterized in that: The zinc salt is one of zinc acetate, zinc formate and zinc gluconate or a combination thereof.

4. The method for preparing the zinc oxide / silver molybdate nano-photocatalytic material according to any one of claims 1 to 3, characterized in that: Prepare as follows: (1) Ammonium molybdate, silver oxide, and zinc acetate were thoroughly mixed in a stoichiometric molar ratio of 1:2:0.1 and ground in a mortar to obtain a mixture A; (2) The obtained mixture A was transferred to a 20 ml glass vial, into which another 3 ml open vial containing 1 ml of distilled water was added; then, the entire container was reacted in an oven at 80 °C for 24 h, the vial was taken out, dried at the same temperature for 12 h, and then re-ground to obtain powder B; (3) Powder B was placed in a muffle furnace and heated to 350°C at a heating rate of 1°C / min and calcined for 4 h to obtain the final product, zinc oxide / silver molybdate nano-photocatalytic material.

5. The method for preparing the zinc oxide / silver molybdate nano-photocatalytic material according to any one of claims 1 to 3, characterized in that: Prepare as follows: (1) Molybdenum trioxide, silver oxide, and zinc formate were thoroughly mixed in a stoichiometric molar ratio of 1:2:0.2 and ground in a mortar to obtain a mixture A; (2) The obtained mixture A was transferred to a 20 ml glass vial, into which another 3 ml open vial containing 1 ml of distilled water was added; after the entire container was reacted in an oven at 70 °C for 30 h, the vial was taken out, dried at the same temperature for 18 h, and then re-ground to obtain powder B; (3) Powder B was placed in a muffle furnace and heated to 400°C at a heating rate of 2°C / min for calcination for 3 h to obtain the final product, zinc oxide / silver molybdate nanophotocatalytic material.

6. The method for preparing the zinc oxide / silver molybdate nano-photocatalytic material according to any one of claims 1 to 3, characterized in that: Prepare as follows: (1) Ammonium molybdate, silver oxide, and zinc gluconate were thoroughly mixed in a stoichiometric molar ratio of 1:2:0.3 and ground in a mortar to obtain a mixture A; (2) The obtained mixture A was transferred to a 20 ml glass vial, into which another 3 ml open vial containing 1 ml of distilled water was added; after the entire container was reacted in an oven at 80 °C for 30 h, the vial was taken out, dried at the same temperature for 12 h, and then re-ground to obtain powder B; (3) Powder B was placed in a muffle furnace and heated to 500°C at a heating rate of 2°C / min for calcination for 2 h to obtain the final product, zinc oxide / silver molybdate nanophotocatalytic material.

7. A zinc oxide / silver molybdate nano-photocatalytic material, prepared according to the method according to any one of claims 1 to 6.

8. Use of the zinc oxide / silver molybdate nano-photocatalytic material according to claim 7 in the degradation treatment of methyl orange in dye wastewater.

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