A high-efficiency H3PMo 12 O 40 / MgIn2S4 composite photocatalyst and its preparation method and application

Abstract

The present invention discloses a high-efficiency H3PMo 12 O 40 The invention relates to the technical field of photocatalytic materials, and the preparation method comprises the following steps: (1) adding magnesium chloride, indium chloride and thioacetamide to deionized water in sequence, mixing and stirring to obtain a suspension; (2) adding H3PMo to the suspension; 12 O 40 Then a hydrothermal reaction is carried out to obtain a precipitate, which is H3PMo 12 O 40 / MgIn2S4 composite photocatalyst. The present invention adopts Keggin type heteropoly acid H3PMo 12 O 40 The catalyst obtained by modifying the flower-shaped MgIn2S4 has the characteristics of stable structure, good dispersibility and adsorption, which is conducive to the transmission of electrons.

Description

Technical Field

[0001] The present invention relates to the technical field of photocatalytic materials, and in particular to a high-efficiency H3PMo 12 O 40 / MgIn2S4 composite photocatalyst and its preparation method and application. Background Art

[0002] Semiconductor photocatalytic water splitting for hydrogen evolution is an advanced technology that uses sunlight as the driving force for the reaction through photocatalysts, converting inexhaustible solar energy into chemical energy. This technology can transform many harsh chemical reactions into mild reactions at room temperature and pressure. It has the advantages of high photocatalytic degradation efficiency, complete degradation of organic pollutants, no residual residue after the reaction, and no secondary pollution.

[0003] As a member of the AB2X4 family of semiconductor bimetallic sulfides, indium magnesium sulfide (InMS) has attracted widespread attention as a promising visible-light-responsive photocatalyst due to its narrow bandgap, unique electronic structure, and excellent visible-light response. However, the photocatalytic performance of InMS is limited by the common shortcomings of sulfides, such as susceptibility to photocorrosion and structural instability.

[0004] Therefore, providing a composite photocatalyst with high catalytic activity, excellent stability and a simple and quick preparation process is a technical problem that needs to be solved urgently in this field. Summary of the Invention

[0005] The purpose of this invention is to provide a H3PMo with high efficiency photocatalytic performance and excellent stability. 12 O 40 / MgIn2S4 composite photocatalyst solves the problems of the prior art pointed out in the background technology.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] A high-efficiency H3PMo 12 O 40 / MgIn2S4 composite photocatalyst, the composite photocatalyst is a Keggin type heteropoly acid H3PMo 12 O 40 Modified flower-shaped MgIn2S4 is obtained.

[0008] Preferably, the diameter of the composite photocatalyst is 2 μm.

[0009] Preferably, the H3PMo 12 O 40 The mass ratio of the MgIn2S4 to the MgIn2S4 is 0.075-0.175.

[0010] Preferably, the H3PMo 12 O 40 The mass ratio of MgIn2S4 to the MgIn2S4 is 0.125.

[0011] According to the above-mentioned high efficiency H3PMo 12 O 40 The preparation method of the composite photocatalyst of MgIn2S4 comprises the following specific steps:

[0012] (1) adding magnesium chloride, indium chloride and thioacetamide to deionized water in sequence and mixing and stirring to obtain a suspension;

[0013] (2) Adding H3PMo to the suspension 12 O 40 Then a hydrothermal reaction is carried out to obtain a precipitate, which is H3PMo 12 O 40 / MgIn2S4 composite photocatalyst.

[0014] Preferably, the molar ratio of the magnesium chloride, the indium chloride and the thioacetamide in step (1) is 1:2:4;

[0015] The molar volume of the magnesium chloride and the deionized water is 1 mmol:40 ml;

[0016] The stirring time is 2h.

[0017] Preferably, the H3PMo in step (2) 12 O 40 By 12 O 40 Prepared by drying xH2O at 80°C for 12 h.

[0018] Preferably, the hydrothermal reaction in step (2) is carried out at 180° C. for 12 h.

[0019] Preferably, the precipitate in step (2) is washed with deionized water and anhydrous ethanol in sequence and then dried.

[0020] As mentioned above, high efficiency H3PMo 12 O 40 Application of / MgIn2S4 composite photocatalyst in photocatalytic water splitting to produce hydrogen

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] (1) H3PMo of the present invention 12 O 40 / MgIn2S4 composite photocatalyst has the characteristics of stable structure, good dispersibility and adsorption, which is conducive to the transmission of electrons; the H3PMo 12 O 40 / MgIn2S4 composite photocatalyst is also easy to recycle and easy to operate;

[0023] (2) The preparation method of the present invention is simple and low-cost. The prepared H3PMo 12 O 40 The MgIn2S4 composite photocatalyst has excellent photocatalytic performance in decomposing water to produce hydrogen under visible light, with a hydrogen production capacity of up to 232.53 μmol·g -1 ·h -1 . BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. The drawings in this description are merely embodiments of the present invention.

[0025] Figure 1 3H3PMo of the present invention 12 O 40 XRD spectrum of / MgIn2S4 composite photocatalyst;

[0026] Figure 2 Example 1-5H3PMo of the present invention 12 O 40 / MgIn2S4 composite photocatalyst hydrogen production performance diagram;

[0027] Figure 3 3H3PMo of the present invention 12 O 40 / MgIn2S4 composite photocatalyst hydrogen production performance cycle diagram;

[0028] Figure 4 3H3PMo of the present invention 12 O 40 XRD comparison of hydrogen production performance of / MgIn2S4 composite photocatalyst before and after;

[0029] Figure 5 3H3PMo of the present invention 12 O 40 SEM image of / MgIn2S4 composite photocatalyst. DETAILED DESCRIPTION

[0030] The following describes embodiments of the present invention, examples of which are shown in the accompanying drawings. The embodiments described with reference to the accompanying drawings are exemplary and intended to be used to explain the present invention, but are not to be construed as limiting the present invention.

[0031] Example 1

[0032] A high-efficiency H3PMo 12 O 40 / MgIn2S4 composite photocatalyst, the preparation method specifically includes the following steps:

[0033] (1) Dissolve 1 mmol of MgCl2·6H2O, 2 mmol of InCl3, and 4 mmol of thioacetamide in 40 mL of deionized water and stir for 2 h to form a transparent suspension.

[0034] (2) H3PMo 12 O 40 After xH2O was dried at 80℃ for 12h, 0.029g H3PMo was weighed 12 O 40 , added to the transparent suspension and continued stirring for 30 minutes, then transferred the solution to a 50ml reactor and reacted in an oven at 180°C for 12 hours. After completion, the reactor was cooled to room temperature to obtain a precipitate, which was washed with deionized water and anhydrous ethanol and dried to obtain H3PMo with high photocatalytic performance. 12 O 40 / MgIn2S4 composite photocatalyst.

[0035] Example 2

[0036] A high-efficiency H3PMo 12 O 40 / MgIn2S4 composite photocatalyst, the preparation method specifically includes the following steps:

[0037] (1) Dissolve 1 mmol of MgCl2·6H2O, 2 mmol of InCl3, and 4 mmol of thioacetamide in 40 mL of deionized water and stir for 2 h to form a transparent suspension.

[0038] (2) H3PMo 12 O 40 ·xH2O was dried at 80℃ for 12h, and 0.038H3PMo was weighed. 12 O 40 , added to the transparent suspension and continued stirring for 30 minutes, then transferred the solution to a 50ml reactor and reacted in an oven at 180°C for 12 hours. After completion, the reactor was cooled to room temperature to obtain a precipitate, which was washed with deionized water and anhydrous ethanol and dried to obtain H3PMo with high photocatalytic performance. 12 O40 / MgIn2S4 composite photocatalyst.

[0039] Example 3

[0040] A high-efficiency H3PMo 12 O 40 / MgIn2S4 composite photocatalyst, the preparation method specifically includes the following steps:

[0041] (1) Dissolve 1 mmol of MgCl2·6H2O, 2 mmol of InCl3, and 4 mmol of thioacetamide in 40 mL of deionized water and stir for 2 h to form a transparent suspension.

[0042] (2) H3PMo 12 O 40 After xH2O was dried at 80℃ for 12h, 0.048g H3PMo was weighed 12 O 40 , added to the transparent suspension and continued stirring for 30 minutes, then transferred the solution to a 50ml reactor and reacted in an oven at 180°C for 12 hours. After completion, the reactor was cooled to room temperature to obtain a precipitate, which was washed with deionized water and anhydrous ethanol and dried to obtain H3PMo with high photocatalytic performance. 12 O 40 / MgIn2S4 composite photocatalyst.

[0043] Example 4

[0044] A high-efficiency H3PMo 12 O 40 / MgIn2S4 composite photocatalyst, the preparation method specifically includes the following steps:

[0045] (1) Dissolve 1 mmol of MgCl2·6H2O, 2 mmol of InCl3, and 4 mmol of thioacetamide in 40 mL of deionized water and stir for 2 h to form a transparent suspension.

[0046] (2) H3PMo 12 O 40 After xH2O was dried at 80℃ for 12h, 0.057g H3PMo was weighed 12 O 40 , added to the transparent suspension and continued stirring for 30 minutes, then transferred the solution to a 50ml reactor and reacted in an oven at 180°C for 12 hours. After completion, the reactor was cooled to room temperature to obtain a precipitate, which was washed with deionized water and anhydrous ethanol and dried to obtain H3PMo with high photocatalytic performance. 12 O 40 / MgIn2S4 composite photocatalyst.

[0047] Example 5

[0048] A high-efficiency H3PMo 12 O 40 / MgIn2S4 composite photocatalyst, the preparation method specifically includes the following steps:

[0049] (1) Dissolve 1 mmol of MgCl2·6H2O, 2 mmol of InCl3, and 4 mmol of thioacetamide in 40 mL of deionized water and stir for 2 h to form a transparent suspension.

[0050] (2) H3PMo 12 O 40 After xH2O was dried at 80℃ for 12h, 0.067g H3PMo was weighed 12 O 40 , added to the transparent suspension and continued stirring for 30 minutes, then transferred the solution to a 50ml reactor and reacted in an oven at 180°C for 12 hours. After completion, the reactor was cooled to room temperature to obtain a precipitate, which was washed with deionized water and anhydrous ethanol and dried to obtain H3PMo with high photocatalytic performance. 12 O 40 / MgIn2S4 composite photocatalyst.

[0051] Figure 2 Example 31-5H3PMo of the present invention 12 O 40 The hydrogen production performance of the MgIn2S4 composite photocatalyst is shown in the graph. It can be seen that the prepared composite photocatalyst has excellent photocatalytic water decomposition and hydrogen evolution performance when 20 mg of the catalyst is dispersed in a 10 ml mixture of lactic acid and water and irradiated by a 300W xenon lamp with a 420nm filter. After 5 hours of reaction, the hydrogen production performance is as high as 1162.65 μmol·g -1 ;

[0052] Figure 3 3H3PMo of the present invention 12 O 40 The hydrogen production performance cycle diagram of the / MgIn2S4 composite photocatalyst. It can be seen from the figure that the prepared composite photocatalyst can maintain good hydrogen production performance after four cycles under the same test method mentioned above.

[0053] Figure 4 3H3PMo of the present invention 12 O 40 The XRD comparison diagram of the hydrogen production performance of the / MgIn2S4 composite photocatalyst before and after the reaction shows no obvious change, indicating that the composite catalyst has good stability.

[0054] Comparative Example 1-2

[0055] Example 3 and other Keggin-type heteropoly acids (mass ratio of 0.125) were tested using the same photocatalytic water decomposition and hydrogen evolution performance test method under the same conditions. The hydrogen production was compared in Table 1 below:

[0056] Table 1 Test results of catalytic performance of different types of Keggin-type heteropolyacids

[0057] Polyacid type <![CDATA[Hydrogen production amount / μmol·g -1 ·h -1 > <![CDATA[H3PW 12 SHE 40 ·xH2O]]> 140.2 <![CDATA[H3PMo 12 SHE 40 ·xH2O]]> 232.5 <![CDATA[H4Si4W 12 SHE 40 ·xH2O]]> 120.7

[0058] As can be seen from the above, compared with other Keggin-type heteropoly acids, the Keggin-type phosphomolybdic acid of the present invention has better performance in photocatalytic water decomposition and hydrogen production.

[0059] Comparative Examples 3-6

[0060] The same preparation method and parameters as in Example 1 were used, with the only difference being that H3PMo 12 O 40 The amount of H3PMo 12 O 40 The mass ratio of MgIn2S4 to MgIn2S4 is not between 0.075 and 0.125. The same photocatalytic water decomposition hydrogen evolution performance test method was used for testing under the same conditions. The hydrogen production was compared in Table 2:

[0061] Table 2 Other proportions of H3PMo 12 O 40 / MgIn2S4 composite photocatalytic performance test results

[0062] Different proportions / % <![CDATA[Hydrogen production amount / μmol·g -1 ·h -1 > 2 23.64 5 67.85 20 105.03 30 25.79

[0063] From the above, we can see that when changing H3PMo 12 O 40 If the mass ratio of MgIn2S4 to MgIn2S4 is not within the range of 0.075-0.125 protected by the present invention, the performance of photocatalytic water decomposition and hydrogen production will be significantly reduced.

[0064] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A high-efficiency H3PMo 12 O 40 / MgIn2S4 composite photocatalyst, characterized in that The composite photocatalyst is a Keggin type heteropoly acid H3PMo 12 O 40 Modified flower ball MgIn2S4 to obtain the H3PMo 12 O 40 The mass ratio of the MgIn2S4 is 0.075-0.175; The preparation method of the composite photocatalyst comprises the following specific steps: (1) adding magnesium chloride, indium chloride and thioacetamide to deionized water in sequence and mixing and stirring to obtain a suspension; (2) Adding H3PMo to the suspension 12 O 40 Then a hydrothermal reaction is carried out to obtain a precipitate, which is H3PMo 12 O 40 / MgIn2S4 composite photocatalyst.

2. A high-efficiency H3PMo according to claim 1 12 O 40 / MgIn2S4 composite photocatalyst, characterized in that The diameter of the composite photocatalyst is 2 μm.

3. A high-efficiency H3PMo according to claim 1 12 O 40 / MgIn2S4 composite photocatalyst, characterized in that The H3PMo 12 O 40 The mass ratio of MgIn2S4 to the MgIn2S4 is 0.

125.

4. A high-efficiency H3PMo according to claim 1 12 O 40 / MgIn2S4 composite photocatalyst, characterized in that The molar ratio of the magnesium chloride, the indium chloride and the thioacetamide in step (1) is 1:2:4; The molar volume of the magnesium chloride and the deionized water is 1 mmol:40 ml; The stirring time is 2h.

5. A high-efficiency H3PMo according to claim 1 12 O 40 / MgIn2S4 composite photocatalyst, characterized in that H3PMo in step (2) 12 O 40 By 12 O 40 Prepared by drying xH2O at 80°C for 12 h.

6. A high-efficiency H3PMo according to claim 1 12 O 40 / MgIn2S4 composite photocatalyst, characterized in that The hydrothermal reaction conditions in step (2) are 180° C. for 12 h.

7. A high-efficiency H3PMo according to claim 1 12 O 40 / MgIn2S4 composite photocatalyst, characterized in that The precipitate in step (3) is washed with deionized water and anhydrous ethanol in sequence and then dried.

8. The highly efficient H3PMo according to any one of claims 1 to 7 12 O 40 Application of / MgIn2S4 composite photocatalyst in photocatalytic water splitting to produce hydrogen.

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