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

Abstract

The application discloses a preparation method of a hydrogen molybdenum bronze-sulfur indium zinc composite photocatalyst and belongs to the technical field of nanometer material preparation. Sodium molybdate is used as a precursor, is dispersed in water, nitric acid is added, and molybdenum trioxide is obtained through aging; then the molybdenum trioxide is dispersed in water, zinc sulfate, indium nitrate and thioacetamide are added, and MoO3-ZIS is obtained through hydrothermal reaction; the obtained MoO3-ZIS is added into an aqueous nitric acid solution, and H x MoO3-ZIS composite is generated through irradiation. The preparation method of the hydrogen molybdenum bronze-sulfur indium zinc composite photocatalyst is simple in preparation process, convenient in operation, 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, there are some reports on the preparation of hydrogen molybdenum bronze. 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 after treatment are placed in the hydrogen molybdenum bronze sol, ultrasonic oscillation is uniformly performed, and then evaporation drying and vacuum drying are performed. The method uses carbon nanotubes in the preparation process, so the energy consumption is large, the repeatability is poor, and the amount of single synthesis is limited. Therefore, there is an urgent need to find a cheap, reliable and stable industrial synthesis method.

[0004] As an important photocatalyst, sulfur indium zinc 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 of compounding the sulfur indium zinc with hydrogen molybdenum bronze as a cocatalyst, and the existing related researches also 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 of molybdenum oxide and sulfur indium zinc (MoO3-ZIS) 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:

[0007] S1, dissolve sodium molybdate in water, add nitric acid, stir, age, and obtain molybdenum trioxide;

[0008] S2, disperse the molybdenum trioxide obtained in S1 in water, add zinc sulfate, indium nitrate and thioacetamide to perform hydrothermal reaction, and obtain molybdenum oxide-zinc indium sulfide;

[0009] S3, add the molybdenum oxide-zinc indium sulfide obtained in S2 to water and nitric acid mixture, and obtain hydrogen molybdate bronze-zinc indium sulfide composite through light irradiation.

[0010] 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.

[0011] Preferably, in S1, the stirring temperature is 60-90℃, the aging temperature is 60-90℃, and the aging time is 0.5-3h.

[0012] 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.

[0013] Preferably, in S2, the hydrothermal reaction temperature is 120-200℃, and the hydrothermal reaction time is 15-30h.

[0014] 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%.

[0015] Preferably, in S3, the light irradiation includes sunlight irradiation or artificial light source irradiation, and the light irradiation time is 0.5-4h.

[0016] Therefore, the application adopts the above-mentioned preparation method of hydrogen molybdate bronze-zinc indium sulfide composite photocatalyst, which uses a molybdenum oxide-zinc indium sulfide (MoO3-ZIS) composite 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.

[0017] The technical solutions of the application will be further described in detail below with reference to the drawings and examples. BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1is an X-ray diffraction pattern of the hydrogen molybdenum bronze-sulfur indium zinc composite photocatalyst prepared in Example 1 of the present application.

[0019] Figure 2 is a scanning electron microscope image of the hydrogen molybdenum bronze-sulfur indium zinc composite photocatalyst prepared in Example 1 of the present application. DETAILED DESCRIPTION

[0020] The technical solutions of the present application are further described below through the drawings and examples.

[0021] Unless otherwise defined, the technical terms or scientific terms used in the present application shall be understood as the usual meanings understood by those skilled in the art to which the present application belongs.

[0022] In the present application, unless otherwise specified, the test materials and instruments and equipment are conventional test materials in the art, and can be purchased through commercial channels.

[0023] Example 1

[0024] The present application provides a preparation method of a hydrogen molybdenum bronze-sulfur indium zinc composite photocatalyst, comprising the following steps:

[0025] S1, 200mg of sodium molybdate is dissolved in 50mL of water, 3mL of 65% concentrated nitric acid is added, and stirring is performed at 70℃ until it is uniformly dispersed, and then aging is performed at 70℃ for 1h to obtain molybdenum trioxide;

[0026] S2, 40mg of the molybdenum trioxide obtained in S1 is dispersed in 60mL of water, 1mol of zinc sulfate, 1mol of indium nitrate and 1mol of thioacetamide are added, and hydrothermal reaction is performed at 200℃ for 20h to obtain MoO3-ZIS;

[0027] S3, 75mg of the MoO3-ZIS obtained in S2 is added into a mixed solution of 45mL of water and 3mL of 65% concentrated nitric acid, and then light irradiation is performed under sunlight for 2h to obtain H x MoO3-ZIS composite. The yield is 90%.

[0028] Example 2

[0029] The present application provides a preparation method of a hydrogen molybdenum bronze-sulfur indium zinc composite photocatalyst, comprising the following steps:

[0030] S1, 300mg of sodium molybdate is dissolved in 100mL of water, 2mL of 65% concentrated nitric acid is added, and stirring is performed at 80℃ until it is uniformly dispersed, and then aging is performed at 80℃ for 1.5h to obtain molybdenum trioxide;

[0031] 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.

[0032] 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%.

[0033] Example 3

[0034] This invention provides a method for preparing a hydrogen-molybdenum bronze-indium-zinc sulfide composite photocatalyst, comprising the following steps:

[0035] 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;

[0036] 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.

[0037] 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%.

[0038] 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.

[0039] 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.

[0040] Therefore, the application adopts the preparation method of the hydrogen molybdenum bronze-sulfur indium zinc composite photocatalyst, which adopts a composite (MoO3-ZIS) of molybdenum oxide and sulfur indium zinc as a precursor to quickly obtain a hydrogen molybdenum bronze-sulfur indium zinc (H x The method is simple in preparation process, convenient in operation, high in yield, and stable in product performance.

[0041] Finally, it should be noted that: the above examples are only used to illustrate the technical solutions of the present application, but not to limit them, although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that: it can still modify or equivalently replace the technical solutions of the present application, and these modifications or equivalent replacements cannot make the modified technical solutions deviate from the spirit and scope of the technical solutions of the present application.

Claims

1. A method for preparing a hydrogen molybdenum bronze-indium zinc sulfide composite photocatalyst, characterized by comprising the steps of: The method 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 for hydrothermal reaction, and obtaining molybdenum oxide-zinc indium sulfide; S3, adding the molybdenum oxide-zinc indium sulfide obtained in S2 into water and nitric acid mixture, and obtaining molybdenum bronze-sulfur indium zinc composite through light irradiation; 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%; In S3, the light irradiation includes sunlight irradiation or artificial light source irradiation, and the irradiation time is 0.5-4 h.

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

3. The preparation method of the hydrogen molybdenum bronze-sulfur indium 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 0.5-3 h.

4. The preparation method of the hydrogen molybdenum bronze-sulfur indium zinc composite photocatalyst according to claim 1, characterized in that: In S2, the mass-volume ratio of molybdenum trioxide and 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.

5. The preparation method of the hydrogen molybdenum bronze-sulfur indium 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 15-30 h.

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