Preparation method of hydrogen molybdenum bronze-sulfur indium zinc composite photocatalyst

Abstract

The invention discloses a preparation method of a hydrogen molybdenum bronze-sulfur indium zinc composite photocatalyst, and belongs to the technical field of nano material preparation, the preparation method comprises the following steps: using sodium molybdate as a precursor, dispersing in water, adding nitric acid, and aging to obtain molybdenum trioxide; dispersing molybdenum trioxide in water, adding zinc sulfate, indium nitrate and thioacetamide, and carrying out hydrothermal reaction to obtain MoO3-ZIS; and adding the obtained MoO3-ZIS into a nitric acid aqueous solution, and carrying out illumination to generate the HxMoO3-ZIS compound. The preparation method of the hydrogen molybdenum bronze-sulfur indium zinc composite photocatalyst is simple in preparation process, convenient to operate, high in yield and stable in product performance.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of nanomaterial preparation, in particular to a preparation method of a hydrogen molybdenum bronze-sulfur indium zinc composite photocatalyst. BACKGROUND

[0002] Hydrogen molybdenum bronze is a hydrogen ion doped metal oxide with high stability and deep blue metallic luster, which is generally represented by H x MoO3 and exhibits the properties of a metal conductor or a semiconductor. The color and performance of the hydrogen molybdenum bronze change with the oxygen vacancy doping concentration. The hydrogen molybdenum bronze has a wide application prospect in multiple fields due to good energy storage and photocatalytic properties.

[0003] At present, some methods for preparing hydrogen molybdenum bronze have been reported. Patent CN201310611648.8 discloses a synthesis method of reduced ammonium molybdenum bronze. In the method, ammonium molybdate is used as a molybdenum source, concentrated hydrochloric acid and formaldehyde are added to form a sol-gel, and then vacuum drying is performed. The method has the problems of long synthesis time, low yield and high cost. Patent CN201611217854.0 discloses that concentrated hydrochloric acid and formaldehyde are added to ammonium molybdate to form a hydrogen molybdenum bronze sol-gel, carbon nanotubes treated are placed in the hydrogen molybdenum bronze sol, and then ultrasonic oscillation is performed. The carbon nanotubes are uniformly dispersed in the hydrogen molybdenum bronze sol, and then the hydrogen molybdenum bronze sol is evaporated and dried in vacuum. The method uses carbon nanotubes in the preparation process, and therefore has the problems of large energy consumption, poor repeatability and limited amount of single synthesis. Therefore, there is an urgent need to find a cheap, reliable and stable industrial synthesis method.

[0004] Sulfur indium zinc is an important photocatalyst and has unique electrical, optical, magnetic and luminescent properties. However, the transmission and separation efficiency of internal photo-generated charges is low, and the bulk phase recombination of electron and hole pairs is serious, thereby greatly reducing the photocatalytic performance of the sulfur indium zinc. At present, in the research on improving the photocatalytic activity of the sulfur indium zinc by compounding with noble metal, graphene and other cocatalysts, there are few studies on the system in which hydrogen molybdenum bronze is used as a cocatalyst to be compounded with the sulfur indium zinc, and the existing related researches still have the problem of complex preparation process of the hydrogen molybdenum bronze. SUMMARY

[0005] The application aims to provide a preparation method of a hydrogen molybdenum bronze-sulfur indium zinc composite photocatalyst. The method uses a composite (MoO3-ZIS) of molybdenum oxide and sulfur indium zinc as a precursor, and quickly obtains a hydrogen molybdenum bronze-sulfur indium zinc (H x MoO3-ZIS) composite under the assistance of light and nitric acid. The method has the advantages of simple preparation process, convenient operation, high yield and stable product performance.

[0006] To achieve the above-mentioned purpose, the application provides a preparation method of a hydrogen molybdenum bronze-sulfur indium zinc composite photocatalyst, which comprises the following steps: S1, dissolving sodium molybdate in water, adding nitric acid, stirring, aging and obtaining molybdenum trioxide; S2, dispersing the molybdenum trioxide obtained in S1 in water, adding zinc sulfate, indium nitrate and thioacetamide to perform a hydrothermal reaction, and obtaining molybdenum oxide-zinc indium sulfide; S3, adding the molybdenum oxide-zinc indium sulfide obtained in S2 in water and nitric acid, and obtaining a hydrogen molybdate bronze-zinc indium sulfide composite through light irradiation.

[0007] Preferably, in S1, the mass-volume ratio of sodium molybdate to water is 200-300 mg: 50-80 mL, the concentration of nitric acid is 65-68%, and the volume-mass ratio of nitric acid to sodium molybdate is 1.5-3 mL: 200-300 mg.

[0008] Preferably, in S1, the stirring temperature is 60-90°C, the aging temperature is 60-90°C, and the aging time is 0.5-3h.

[0009] Preferably, in S2, the mass-volume ratio of molybdenum trioxide to water is 40-60 mg: 60-100 mL, and the molar-volume ratio of zinc sulfate, indium nitrate, thioacetamide and water is 1-2 mol: 1-2 mol: 1-2 mol: 60-100 mL.

[0010] Preferably, in S2, the hydrothermal reaction temperature is 120-200°C, and the hydrothermal reaction time is 15-30h.

[0011] Preferably, in S3, the mass-volume ratio of molybdenum oxide-zinc indium sulfide, water and nitric acid is 60-100 mg: 45-50 mL: 3-4 mL, and the concentration of nitric acid is 65-68%.

[0012] Preferably, in S3, the light irradiation includes sunlight irradiation or artificial light source irradiation, and the light irradiation time is 0.5-4h.

[0013] Therefore, the present application adopts the above-mentioned preparation method of the hydrogen molybdate bronze-zinc indium sulfide composite photocatalyst, which uses a molybdenum oxide-zinc indium sulfide composite (MoO3-ZIS) as a precursor to quickly obtain a hydrogen molybdate bronze-zinc indium sulfide (H x MoO3-ZIS) composite under the assistance of light irradiation and nitric acid. The method has simple preparation process, convenient operation, high yield and stable product performance.

[0014] The technical solutions of the present application will be further described in detail below through the accompanying drawings and examples. BRIEF DESCRIPTION OF DRAWINGS

[0015] Figure 1 is the X-ray diffraction pattern of the hydrogen molybdate bronze-zinc indium sulfide composite photocatalyst prepared in Example 1 of the present application; Figure 2 is the scanning electron microscope image of the hydrogen molybdate bronze-zinc indium sulfide composite photocatalyst prepared in Example 1 of the present application. Detailed Implementation

[0016] The technical solution of the present invention will be further described below with reference to the accompanying drawings and embodiments.

[0017] Unless otherwise defined, the technical or scientific terms used in this invention shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention pertains.

[0018] In this invention, unless otherwise specified, the test materials and instruments are all conventional test materials in the field and can be purchased through commercial channels.

[0019] Example 1 This invention provides a method for preparing a hydrogen-molybdenum bronze-indium-zinc sulfide composite photocatalyst, comprising the following steps: S1. Dissolve 200 mg of sodium molybdate in 50 mL of water, add 3 mL of 65% nitric acid, stir and disperse evenly at 70 °C, and age at 70 °C for 1 h to obtain molybdenum trioxide; S2. Take 40 mg of molybdenum trioxide obtained in S1 and disperse it in 60 mL of water. Add 1 mol of zinc sulfate, 1 mol of indium nitrate and 1 mol of thioacetamide. Perform a hydrothermal reaction at 200 °C for 20 h to obtain MoO3-ZIS. S3. Take 75 mg of MoO3-ZIS obtained in S2, add it to a mixed solution of 45 mL water and 3 mL 65% nitric acid, and irradiate under sunlight for 2 hours to obtain H. x MoO3-ZIS complex. Yield: 90%.

[0020] Example 2 This invention provides a method for preparing a hydrogen-molybdenum bronze-indium-sulfur zinc composite photocatalyst, comprising the following steps: S1. Dissolve 300 mg of sodium molybdate in 100 mL of water, add 2 mL of 65% nitric acid, stir and disperse evenly at 80 °C, and age at 80 °C for 1.5 h to obtain molybdenum trioxide; S2. Take 60 mg of molybdenum trioxide obtained in S1 and disperse it in 80 mL of water. Add 1.5 mol zinc sulfate, 1.5 mol indium nitrate and 1.5 mol thioacetamide. Perform a hydrothermal reaction at 180 °C for 24 h to obtain MoO3-ZIS. S3. Take 100 mg of MoO3-ZIS obtained in S2, add it to a mixed solution of 50 mL water and 4 mL 65% nitric acid, and irradiate under sunlight for 0.5 h to obtain H. x MoO3-ZIS complex. Yield: 88%.

[0021] Example 3 This invention provides a method for preparing a hydrogen-molybdenum bronze-indium-zinc sulfide composite photocatalyst, comprising the following steps: S1. Dissolve 200 mg of sodium molybdate in 80 mL of water, add 1.5 mL of 65% nitric acid, stir and disperse evenly at 80 °C, and age at 80 °C for 2 h to obtain molybdenum trioxide; S2. Take 45 mg of molybdenum trioxide obtained in S1 and disperse it in 100 mL of water. Add 2 mol of zinc sulfate, 2 mol of indium nitrate and 2 mol of thioacetamide. Perform a hydrothermal reaction at 180 °C for 18 h to obtain MoO3-ZIS. S3. Take 60 mg of MoO3-ZIS obtained in S2, add it to a mixed solution of 50 mL water and 4 mL 65% nitric acid, and irradiate under sunlight for 1 hour to obtain H. x MoO3-ZIS complex. Yield 85%.

[0022] The hydrogen molybdenum bronze-indium sulfide zinc prepared in Example 1 was characterized by X-ray diffraction (XRD), and the results are as follows: Figure 1 As shown, from Figure 1 As can be seen from the data, the XRD diffraction peaks are attributed to hydrogen molybdenum bronze and indium sulfide zinc, respectively, indicating that the hydrogen molybdenum bronze-indium sulfide zinc composite material was successfully prepared.

[0023] The hydrogen molybdenum bronze-indium sulfide zinc prepared in Example 1 was characterized by scanning electron microscopy, and the results are as follows: Figure 2 As shown, from Figure 2 As can be seen, indium zinc sulfide is spherical composed of nanosheets, while molybdenum bronze is rod-shaped, and indium zinc sulfide is successfully grown on the surface of molybdenum bronze nanorods.

[0024] Therefore, this invention employs the above-mentioned method for preparing a hydrogen molybdenum bronze-indium zinc sulfide composite photocatalyst, which uses a composite of molybdenum oxide and zinc sulfide (MoO3-ZIS) as a precursor to rapidly obtain hydrogen molybdenum bronze-indium zinc sulfide (H) under the assistance of light and nitric acid. x The method for preparing the MoO3-ZIS complex is simple, convenient, has a high yield, and produces stable product performance.

[0025] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the technical solutions of the present invention, and these modifications or equivalent substitutions cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A method for preparing a hydrogen-molybdenum bronze-indium-sulfur zinc composite photocatalyst, characterized in that: Includes the following steps: S1. Dissolve sodium molybdate in water, add nitric acid, stir, and age to obtain molybdenum trioxide; S2. Disperse the molybdenum trioxide obtained in S1 in water, add zinc sulfate, indium nitrate and thioacetamide to carry out hydrothermal reaction to obtain molybdenum oxide-zinc indium sulfide; S3. The molybdenum oxide-indium sulfide zinc obtained in S2 is added to water and nitric acid and mixed. After irradiation, hydrogen molybdenum bronze-indium sulfide zinc complex is obtained.

2. The preparation method of the hydrogen-molybdenum bronze-indium-sulfur zinc composite photocatalyst according to claim 1, characterized in that: In S1, the mass-to-volume ratio of sodium molybdate to water is 200-300 mg: 50-80 mL, the concentration of nitric acid is 65-68%, and the volume-to-mass ratio of nitric acid to sodium molybdate is 1.5-3 mL: 200-300 mg.

3. The preparation method of the hydrogen-molybdenum bronze-indium-sulfur zinc composite photocatalyst according to claim 1, characterized in that: In S1, the stirring temperature is 60-90℃, the aging temperature is 60-90℃, and the aging time is 0.5-3h.

4. The preparation method of the hydrogen-molybdenum bronze-indium-sulfur zinc composite photocatalyst according to claim 1, characterized in that: In S2, the mass-to-volume ratio of molybdenum trioxide to water is 40-60 mg: 60-100 mL, and the molar-to-volume ratio of zinc sulfate, indium nitrate, thioacetamide, and water is 1-2 mol: 1-2 mol: 1-2 mol: 60-100 mL.

5. The preparation method of the hydrogen molybdenum bronze-indium sulfide zinc composite photocatalyst according to claim 1, characterized in that: In S2, the hydrothermal reaction temperature is 120-200℃, and the hydrothermal reaction time is 15-30h.

6. The preparation method of the hydrogen-molybdenum bronze-indium-sulfur zinc composite photocatalyst according to claim 1, characterized in that: In S3, the mass-volume ratio of molybdenum oxide-zinc indium sulfide, water, and nitric acid is 60-100 mg: 45-50 mL: 3-4 mL, and the concentration of nitric acid is 65-68%.

7. The preparation method of the hydrogen-molybdenum bronze-indium-sulfur zinc composite photocatalyst according to claim 1, characterized in that: In S3, illumination includes sunlight or artificial light, and the illumination time is 0.5-4 hours.

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