A MnCo2S4 / Ba x Sr 1-x TiO3 composite catalyst, preparation method and application thereof

Abstract

The application belongs to the field of piezoelectric photocatalysis, and particularly relates to a MnCo2S4 / Ba x Sr 1‑x TiO3 composite catalyst, a preparation method and application thereof. x Sr 1‑x TiO3 is prepared by a two-step high-temperature calcination method, MnCo2S4 is prepared by a one-step hydrothermal synthesis method, and finally, the two are fully contacted and compounded to form a heterojunction by an ultrasonic stirring method, so that the MnCo2S4 / Ba x Sr 1‑x TiO3 composite catalyst is prepared. The synthesis method adopted by the application is simple, the preparation cost is low, and the application is green, environmentally friendly and pollution-free. The catalyst prepared by the application has rich active sites. The catalyst is used for piezoelectric photocatalytic production of H2, and under the synergistic action of light and ultrasonic waves, the catalyst shows stability and excellent H2 production capacity, and the application of Ba x Sr 1‑x TiO3 in the field of piezoelectric photocatalytic hydrogen production is expanded.

Description

Technical Field

[0001] This invention belongs to the field of piezoelectric photocatalysis, specifically relating to a MnCo2S4 / Ba x Sr 1-x TiO3 composite catalysts, their preparation methods, and applications. Background Technology

[0002] Since Fujishima first reported the use of TiO2 semiconductor materials for photocatalytic water splitting, semiconductor photocatalytic hydrogen production has gradually become a research hotspot, and more and more semiconductor materials for photocatalysis have been developed.

[0003] Lead-free barium strontium titanate (Ba x Sr 1-x Strontium barium titanate (STiO3), composed of BaTiO3 and SrTiO3, is a typical perovskite oxide material with excellent ferroelectric / piezoelectric properties. Its application in photocatalysis is illustrated by patent CN112973686A, which discloses a BaTiO3... 1-x Sr x The preparation and application of TiO3 / Ag2O photocatalysts involved using Ba(CH3COO)2, Sr(CH3COO)2, and tetrabutyl titanate as raw materials. After hydrolysis and polycondensation to form a wet gel, the gel was then electrospinned and calcined to prepare BaO3 / Ag2O photocatalysts. 1- x Sr x TiO3 nanotubes were then attached to Ba using an ion adsorption method, along with silver nanoparticles and silver oxide particles. 1-x Sr x On TiO3 nanotubes, S-shaped or Z-shaped heterostructure composite materials Ba were obtained. 1-x Sr x TiO3 / Ag2O photocatalyst, utilizing Ba 1-x Sr x TiO3's pyroelectric effect enhances the photocatalytic performance of catalysts, but the preparation method is cumbersome, the preparation cost is high, and the operation is difficult. However, the catalytic efficiency still needs to be improved. Summary of the Invention

[0004] The purpose of this invention is to provide a MnCo2S4 / Ba x Sr 1-x TiO3 composite catalyst, when applied to piezoelectric photocatalytic H2 production, exhibits higher catalytic activity.

[0005] The MnCo2S4 / Ba provided by this invention x Sr 1-x The TiO3 composite catalyst is prepared by the following steps:

[0006] (1)Bax Sr 1-x Preparation of TiO3:

[0007] Weigh out TiO2, BaCO3, and SrCO3 by molar ratio, place them in an agate mortar, grind for 20–40 minutes, then place them in a tube furnace and heat to 900–1200℃ (preferably 900–1100℃) at a rate of 2℃ / min, calcine for 6 hours. After calcine, allow to cool naturally to room temperature, then grind a second time for 20–40 minutes. Then place them back in the tube furnace and heat to 1000–1300℃ (preferably 1000–1200℃) at a rate of 2℃ / min, calcine for 6 hours. After natural cooling, obtain white BaCO3. x Sr 1-x TiO3.

[0008] Furthermore, the Ba x Sr 1-x In TiO3, x is the molar ratio, 0.2≤x≤0.8 (preferably x=0.5);

[0009] Furthermore, the molar ratio of TiO2, BaCO3, and SrCO3 is 2:x:1-x.

[0010] (2) Preparation of MnCo2S4:

[0011] CH4N2S, MnC4H6O4·4H2O, CoCl2·6H2O, and NaOH were added sequentially to deionized water and stirred for 30 min. The mixture was then transferred to a polytetrafluoroethylene-lined reactor and subjected to hydrothermal reaction in an oven at 180 °C for 12 h. After the reaction was completed, the mixture was allowed to cool naturally to room temperature. The solid in the reactor was washed multiple times with deionized water and ethanol and dried to obtain black MnCo2S4 (abbreviated as MCS).

[0012] Furthermore, the molar ratio of CH4N2S, MnC4H6O4·4H2O, CoCl2·6H2O, and NaOH is 6:1:2:10.

[0013] (3) MnCo2S4 / Ba x Sr 1-x Preparation of TiO3 composite catalyst:

[0014] MnCo2S4 and Ba x Sr 1-x TiO3 was dispersed in a certain amount of solvent, and after ultrasonication, stirring, filtration, washing, and drying, MnCo2S4 / Ba was obtained. x Sr 1-x TiO3 composite catalyst.

[0015] Furthermore, the mass of MnCo2S4 added is Ba x Sr 1-x TiO3 content is 3-7% of the total mass.

[0016] Furthermore, the solvent includes deionized water.

[0017] Furthermore, the ultrasonic power is 240W, and the time is 1 hour; the stirring speed is 400 r / min, and the time is 12 hours.

[0018] The composite catalyst prepared by the above method is used for piezoelectric photocatalytic hydrogen production. The specific application method is as follows: MnCo2S4 / Ba x Sr 1-x TiO3 composite catalyst was added to water and dispersed evenly. Then methanol, a sacrificial agent, was added, followed by the introduction of N2. Under ultrasonic and light irradiation conditions, piezoelectric photocatalytic H2 production was carried out.

[0019] Furthermore, the ultrasonic power is 240W; the illumination is a 55W xenon lamp simulating sunlight.

[0020] Furthermore, the MnCo2S4 / Ba x Sr 1-x The amount of TiO3 composite catalyst used in water is 1-3 mg / 18 mL (preferably 2 mg / 18 mL).

[0021] The beneficial effects of this invention are as follows:

[0022] (1) This invention prepares Ba by a two-step calcination method. x Sr 1-x TiO3 has advantages such as simple preparation method, low cost and easy operation.

[0023] (2) By changing the addition ratio of Ba and Sr, this invention obtained the optimal ratio for piezoelectric photocatalytic performance through performance testing and comparison. 0.5 Sr 0.5 TiO3.

[0024] (3) The addition of co-catalyst MnCo2S4 improves Ba x Sr 1-x TiO3's light absorption capacity enhances the catalyst's response to light, significantly improving the performance of Ba. x Sr 1-x The piezoelectric photocatalytic performance of TiO3 compared to pure MnCo2S4 and Ba 0.5 Sr 0.5 TiO3 improved by 9.45 and 7.57 times.

[0025] (4) Ba relative to wide bandwidth xSr 1-x The addition of TiO3 and narrow-bandgap MnCo2S4 can generate more active photogenerated carriers, promote charge separation and migration, and suppress electron-hole recombination, thereby improving the overall piezoelectric photocatalytic performance.

[0026] (5) Preparation of MnCo2S4 / Ba by a simple ultrasonic stirring method x Sr 1-x TiO3 composite catalysts offer rapid and efficient composite processes that are green and pollution-free.

[0027] (6) This invention extends Ba x Sr 1-x Application of TiO3 in piezoelectric photocatalytic hydrogen production. Attached image description:

[0028] Figure 1 It is the MnCo2S4 / Ba synthesized in Example 1 0.5 Sr 0.5 Scanning electron microscope image of TiO3 composite catalyst;

[0029] Figure 2 MnCo2S4 and Ba synthesized in Comparative Examples 3-4 0.5 Sr 0.5 XRD pattern of TiO3 catalyst;

[0030] Figure 3 The MnCo2S4 / Ba synthesized in Examples 1-5 0.5 Sr 0.5 XRD pattern of TiO3 composite catalyst;

[0031] Figure 4 These are H2 production performance graphs of the catalysts synthesized in Examples 1-5 and Comparative Examples 3-4 under piezoelectric-optical conditions;

[0032] Figure 5 These are performance graphs of the catalysts synthesized in Examples 1-5 and Comparative Examples 3-4 for H2 production under piezoelectric effects only;

[0033] Figure 6 These are performance graphs of the catalysts synthesized in Examples 1-5 and Comparative Examples 3-4 under light-only irradiation for H2 production.

[0034] Figure 7 The graph shows the H2 production performance of the catalysts synthesized in Comparative Examples 3 and 5-8 under piezoelectric-optical conditions. Detailed Implementation

[0035] This invention is not limited to the following specific embodiments. Those skilled in the art can implement this invention using various other specific embodiments based on the content disclosed herein. Any modifications or alterations to the design structure and concept of this invention fall within the protection scope of this invention. It should be noted that, in the absence of conflict, the embodiments and features described in these embodiments can be combined with each other. The H2 production efficiency is calculated using the following formula:

[0036]

[0037] R: H2 production rate, unit: μmol / (g·h)

[0038] V: Volume of hydrogen gas, unit: μL

[0039] m: Catalyst mass, unit: g

[0040] t: reaction time, unit: h.

[0041] Example 1

[0042] (1) Place 0.56g TiO2, 0.69g BaCO3 and 0.52g SrCO3 in an agate bowl, grind for 30 min, then place in a tube furnace and heat to 1000℃ at a rate of 2℃ / min, calcine for 6 h. After calcine, allow to cool naturally to room temperature, grind a second time for 30 min, then place in a tube furnace and heat to 1100℃ at a rate of 2℃ / min, calcine for 6 h. After natural cooling, obtain white BaO2. 0.5 Sr 0.5 TiO3.

[0043] (2) Add 1.370g CH4N2S, 0.735g MnC4H6O4·4H2O, 1.427g CoCl2·6H2O, and 1.2g NaOH to 70ml of deionized water, stir for 30min, and then transfer to a polytetrafluoroethylene-lined reactor. React in an oven at 180℃ for 12h. After the reaction is complete, cool naturally to room temperature. Wash the solid in the reactor with deionized water and ethanol several times, and dry to obtain black MnCo2S4.

[0044] (3) will Ba 0.5 Sr 0.5 TiO3 and MnCo2S4 were dissolved in deionized water, sonicated at 240 W for 1 h, and then stirred at 400 r / min for 12 h. The mixture was then filtered, washed, and dried at room temperature to obtain a gray powder, which is MnCo2S4 / Ba. 0.5 Sr 0.5TiO3 composite catalyst, designated as 5% MnCo2S4-Ba 0.5 Sr 0.5 TiO3. Among them, the mass of MnCo2S4 is Ba. 0.5 Sr 0.5 5% of the TiO3 mass.

[0045] The MnCo2S4 / Ba prepared in Example 1 0.5 Sr 0.5 TiO3 composite catalyst applied to piezoelectric photocatalytic H2 production:

[0046] 2 mg 5% MnCo2S4-Ba 0.5 Sr 0.5 TiO3 and 18 mL of water were mixed and ultrasonically dispersed for 0.5 h to ensure uniform dispersion of the catalyst in the water. Then, 2 mL of methanol was added as a sacrificial agent, followed by N2 purging for 30 min. Finally, the mixture was sealed for 2 h under ultrasonic (240 W) and light irradiation (55 W xenon lamp simulating sunlight). After the experiment, 0.5 mL of gas was extracted from the tube, and the peak area was detected using a gas chromatograph. The H2 production rate was calculated to be 1593.34 μmol / (g·h).

[0047] Example 2:

[0048] Compared with Example 1, the difference is that in step (3), the mass of MnCo2S added is Ba 0.5 Sr 0.5 The TiO3 content was 3% by mass, and other parameters were the same as in Example 1. The resulting composite catalyst was designated as 3% MnCo2S4-Ba 0.5 Sr 0.5 TiO3.

[0049] The 3% MnCo2S4-Ba prepared in Example 2 0.5 Sr 0.5 TiO3 was applied to piezoelectric photocatalysis for H2 production, using the same method as in Example 1, and the H2 production rate was 1206.45 μmol / (g·h).

[0050] Example 3:

[0051] Compared with Example 1, the difference is that in step (3), the mass of MnCo2S added is Ba 0.5 Sr 0.5 The TiO3 content was 4% by mass, and other parameters were the same as in Example 1. The resulting composite catalyst was designated as 4%MnCo2S4-Ba 0.5 Sr 0.5 TiO3.

[0052] The 4% MnCo2S4-Ba prepared in Example 3 0.5Sr 0.5 TiO3 was applied to piezoelectric photocatalysis for H2 production, using the same method as in Example 1, and the H2 production rate was 1423.62 μmol / (g·h).

[0053] Example 4:

[0054] Compared with Example 1, the difference is that in step (3), the mass of MnCo2S added is Ba 0.5 Sr 0.5 The composite catalyst prepared using 6% TiO3 by mass, with other parameters the same as in Example 1, is designated as 6% MnCo2S4-Ba. 0.5 Sr 0.5 TiO3.

[0055] The 6% MnCo2S4-Ba prepared in Example 4 0.5 Sr 0.5 TiO3 was applied to piezoelectric photocatalysis for H2 production, using the same method as in Example 1, and the H2 production rate was 1336.04 μmol / (g·h).

[0056] Example 5:

[0057] Compared with Example 1, the difference is that in step (3), the mass of MnCo2S added is Ba 0.5 Sr 0.5 The composite catalyst prepared using 7% TiO3 by mass, with other parameters the same as in Example 1, is designated as 7% MnCo2S4-Ba. 0.5 Sr 0.5 TiO3.

[0058] The 7% MnCo2S4-Ba prepared in Example 5 0.5 Sr 0.5 TiO3 was applied to piezoelectric photocatalysis for H2 production, using the same method as in Example 1, and the H2 production rate was 1139.59 μmol / (g·h).

[0059] Example 6:

[0060] Compared with Example 1, the difference is that the calcination temperatures of 1000℃ and 1100℃ in step (1) are changed to 1200℃ and 1300℃, respectively; otherwise, they are the same as in Example 1. The prepared composite catalyst is designated as 5%MnCo2S4-1200Ba. 0.5 Sr 0.5 TiO3.5%MnCo2S4-1200Ba 0.5 Sr 0.5 The H2 production rate of the TiO3 catalyst is 746.69 μmol / (g·h).

[0061] Example 7:

[0062] The difference compared to Example 1 is that: MnCo2S4 / Ba 0.5 Sr 0.5 TiO3 composite catalyst applied to piezoelectric photocatalytic H2 production, 5% MnCo2S4-Ba 0.5 Sr 0.5 The amount of TiO3 added was changed to 1 mg. Everything else was the same as in Example 1, and the H2 production rate of the prepared composite catalyst was 1202.35 μmol / (g·h).

[0063] Example 8:

[0064] The difference compared to Example 1 is that: MnCo2S4 / Ba 0.5 Sr 0.5 TiO3 composite catalyst applied to piezoelectric photocatalytic H2 production, 5% MnCo2S4-Ba 0.5 Sr 0.5 The amount of TiO3 added was changed to 3 mg. Everything else was the same as in Example 1, and the H2 production rate of the prepared composite catalyst was 360.62 μmol / (g·h).

[0065] Comparative Example 1

[0066] Compared with Examples 1-5 and Comparative Examples 3-4, the difference is that the ultrasonic (240W) and light (55W xenon lamp simulating sunlight) conditions in the application method were changed to ultrasonic (240W) only. Otherwise, it is the same as Examples 1-5 and Comparative Examples 3-4. The H2 production rate test results are shown in […]. Figure 5 .

[0067] Comparative Example 2

[0068] Compared with Examples 1-5 and Comparative Examples 3-4, the difference is that the ultrasonic (240W) and light-irradiation (55W xenon lamp simulating sunlight) methods were changed to light-irradiation only (55W xenon lamp simulating sunlight). Otherwise, the methods are the same as Examples 1-5 and Comparative Examples 3-4. The H2 production rate test results are shown in [link to relevant documentation]. Figure 6 .

[0069] Comparative Example 3

[0070] 0.56 g TiO2, 0.69 g BaCO3, and 0.52 g SrCO3 were placed on an agate bowl and ground for 30 minutes. Then, the bowl was placed in a tube furnace and heated to 1000 °C at a rate of 2 °C / min for 6 hours. After calcination, the mixture was allowed to cool naturally to room temperature and then ground a second time for 30 minutes. The mixture was then placed in a tube furnace and heated to 1100 °C at a rate of 2 °C / min for 6 hours. After natural cooling, white BaCO3 was obtained. 0.5 Sr 0.5 TiO3.

[0071] Ba prepared in Comparative Example 3 0.5 Sr 0.5 TiO3 catalyst applied to piezoelectric photocatalytic H2 production:

[0072] Weigh out 2mg Ba 0.5 Sr 0.5 TiO3 catalyst was mixed with 18 mL of water and ultrasonically dispersed for 0.5 h. Then, 2 mL of methanol was added as a sacrificial agent, followed by N2 purging for 30 min. Finally, the mixture was sealed for 2 h under ultrasonic (240 W) and light irradiation (55 W xenon lamp simulating sunlight). After the experiment, 0.5 mL of gas was extracted from the tube, and the peak area was detected using a gas chromatograph. The H2 production rate was calculated to be 210.37 μmol / (g·h).

[0073] Comparative Example 4

[0074] 1.370g CH4N2S, 0.735g MnC4H6O4·4H2O, 1.427g CoCl2·6H2O, and 1.2g NaOH were added sequentially to 70ml of deionized water and stirred for 30min. The mixture was then transferred to a polytetrafluoroethylene-lined reactor and hydrothermally reacted in an oven at 180℃ for 12h. After the reaction was completed, the mixture was allowed to cool naturally to room temperature. The solid in the reactor was washed several times with deionized water and ethanol and dried to obtain black MnCo2S4.

[0075] The MnCo2S4 catalyst prepared in Comparative Example 4 was applied to piezoelectric photocatalytic H2 production:

[0076] 2 mg of MnCo2S4 catalyst was weighed and mixed with 18 mL of water, then ultrasonically dispersed for 0.5 h. 2 mL of methanol was then added as a sacrificial agent, followed by N2 purging for 30 min. Finally, the mixture was sealed for 2 h under ultrasonic (240 W) and light irradiation (55 W xenon lamp simulating sunlight). After the experiment, 0.5 mL of gas was extracted from the tube, and the peak area was detected using a gas chromatograph. The H2 production rate was calculated to be 168.63 μmol / (g·h).

[0077] Comparative Example 5

[0078] 0.56g TiO2 and 1.03g SrCO3 were placed on an agate bowl and ground for 30 minutes. Then, the bowl was placed in a tube furnace and heated to 1000℃ at a rate of 2℃ / min for 6 hours. After calcination, the bowl was allowed to cool naturally to room temperature and ground a second time for 30 minutes. The bowl was then placed in a tube furnace and heated to 1100℃ at a rate of 2℃ / min for 6 hours. After natural cooling, white SrTiO3 was obtained.

[0079] The SrTiO3 catalyst prepared in Comparative Example 5 was applied to piezoelectric photocatalytic H2 production:

[0080] 2 mg of SrTiO3 catalyst was weighed and mixed with 18 mL of water, then ultrasonically dispersed for 0.5 h. 2 mL of methanol was added as a sacrificial agent, followed by N2 purging for 30 min. Finally, the mixture was sealed for 2 h under ultrasonic (240 W) and light irradiation (55 W xenon lamp simulating sunlight). After the experiment, 0.5 mL of gas was extracted from the tube, and the peak area was detected using a gas chromatograph. The H2 production rate was calculated to be 98.46 μmol / (g·h).

[0081] Comparative Example 6

[0082] 0.56g TiO2 and 1.38g BaCO3 were placed on an agate bowl and ground for 30 minutes. Then, the bowl was placed in a tube furnace and heated to 1000℃ at a rate of 2℃ / min for 6 hours. After calcination, the bowl was allowed to cool naturally to room temperature and ground a second time for 30 minutes. The bowl was then placed in a tube furnace and heated to 1100℃ at a rate of 2℃ / min for 6 hours. After natural cooling, white BaTiO3 was obtained.

[0083] The BaTiO3 catalyst prepared in Comparative Example 6 was applied to piezoelectric photocatalytic H2 production:

[0084] 2 mg of BaTiO3 catalyst was weighed and mixed with 18 mL of water, then ultrasonically dispersed for 0.5 h. 2 mL of methanol was added as a sacrificial agent, followed by N2 purging for 30 min. Finally, the mixture was sealed for 2 h under ultrasonic (240 W) and light irradiation (55 W xenon lamp simulating sunlight). After the experiment, 0.5 mL of gas was extracted from the tube, and the peak area was detected using a gas chromatograph. The H2 production rate was calculated to be 57.31 μmol / (g·h).

[0085] Comparative Example 7

[0086] Compared with Example 1, the difference is that in step (1), the added BaCO3 and SrCO3 are 0.28g and 0.83g respectively, and the rest is the same as in Example 1. The catalyst prepared is denoted as Ba. 0.2 Sr 0.8 TiO3.

[0087] Ba prepared in Comparative Example 7 0.2 Sr 0.8 TiO3 was applied to piezoelectric photocatalysis for H2 production, using the same method as in Example 1, and the H2 production rate was 98.96 μmol / (g·h).

[0088] Comparative Example 8

[0089] Compared with Example 1, the difference is that in step (1), the added BaCO3 and SrCO3 are 1.10g and 0.21g respectively, and the rest is the same as in Example 1. The catalyst prepared is denoted as Ba. 0.8 Sr 0.2 TiO3.

[0090] Ba prepared in Comparative Example 8 0.8 Sr 0.2 TiO3 was applied to piezoelectric photocatalysis for H2 production, using the same method as in Example 1, and the H2 production rate was 74.60 μmol / (g·h).

[0091] Comparative Example 9:

[0092] Compared with Example 1, the difference is that the calcination temperatures of 1000℃ and 1100℃ in step (1) are changed to 800℃ and 900℃, respectively; otherwise, they are the same as in Example 1. The prepared composite catalyst is denoted as 5%MnCo2S4-800Ba. 0.5 Sr 0.5 TiO3.5% MnCo2S4-800 Ba 0.5 Sr 0.5 The H2 production rate of TiO3 is 52.02 μmol / (g·h).

[0093] Based on the above-described preferred embodiments of the present invention, and through the foregoing description, those skilled in the art can make various changes and modifications without departing from the inventive concept. The technical scope of this invention is not limited to the contents of the specification, but must be determined according to the scope of the claims.

Claims

1. A MnCo2S4 / BaO2 composite for piezoelectric photocatalytic H2 production x Sr 1-x The TiO3 composite catalyst is characterized by... Composed of MnCo2S4 and Ba x Sr 1-x TiO3 composites form a heterostructure; the MnCo2S4 is Ba x Sr 1-x 3-7% of TiO3 by mass; the Ba x Sr 1-x In TiO3, x represents the molar ratio, 0.2 <x<0.8; The Ba x Sr 1-x The preparation method of TiO3 is as follows: Weigh TiO2, BaCO3, and SrCO3, then place them in an agate mortar and grind for 20-40 minutes. Next, place the mortar in a tube furnace and heat to 900-1200 °C at a rate of 2 °C / min, calcining for 6 hours. After calcination, allow it to cool naturally to room temperature and grind a second time for 20-40 minutes. Then, place the mortar in the tube furnace again and heat to 1000-1300 °C at a rate of 2 °C / min, calcining for 6 hours. After natural cooling, white BaCO3 is obtained. x Sr 1-x TiO3.

2. A MnCo2S4 / Ba as described in claim 1 x Sr 1-x The method for preparing TiO3 composite catalyst is characterized by, The steps include: mixing MnCo2S4 and Ba x Sr 1-x TiO3 was dispersed in deionized water, and after ultrasonic and stirring treatment, it was filtered, washed, and dried to obtain MnCo2S4 / Ba x Sr 1-x TiO3 composite catalyst.

3. The MnCo2S4 / Ba according to claim 2 x Sr 1-x The method for preparing TiO3 composite catalyst is characterized by, The ultrasonic power is 240 W, the ultrasonic time is 1 h, the stirring speed is 400 r / min, and the stirring time is 12 h.

4. The MnCo2S4 / Ba according to claim 2 x Sr 1-x The method for preparing TiO3 composite catalyst is characterized by, The preparation method of MnCo2S4 is as follows: CH4N2S, MnC4H6O4·4H2O, CoCl2·6H2O, and NaOH were added sequentially to deionized water and stirred for 30 min. The mixture was then transferred to a polytetrafluoroethylene-lined reactor and reacted in an oven at 180°C for 12 h. After the reaction was completed, the mixture was allowed to cool naturally to room temperature. The solid in the reactor was washed several times with deionized water and ethanol and dried to obtain black MnCo2S4.

5. The MnCo2S4 / Ba according to claim 4 x Sr 1-x The method for preparing TiO3 composite catalyst is characterized by, The molar ratio of CH4N2S, MnC4H6O4·4H2O, CoCl2·6H2O, and NaOH is 6:1:2:

10.

6. A MnCo2S4 / Ba as described in claim 1 x Sr 1-x The application of TiO3 composite catalyst in piezoelectric photocatalytic H2 production is characterized by... MnCo2S4 / Ba x Sr 1-x TiO3 composite catalyst was added to water and dispersed evenly. Then methanol, a sacrificial agent, was added, followed by the introduction of N2. Under ultrasonic and light irradiation conditions, piezoelectric photocatalytic H2 production was carried out.

7. The application according to claim 6, characterized in that, The ultrasonic power is 240 W; the illumination is a 55 W xenon lamp simulating sunlight.

8. The application according to claim 6, characterized in that, The MnCo2S4 / Ba x Sr 1-x The dosage of TiO3 composite catalyst in water is 1~3 mg / 18 mL.

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