Copper-doped cadmium zinc sulfide / chromium-doped bismuth vanadate hollow sphere composite photocatalyst as well as preparation method and application thereof
By modifying the surface of chromium-doped bismuth vanadate hollow spheres with copper-doped zinc cadmium sulfide nanoparticles, a composite photocatalyst was formed, which solved the problem of low photocatalytic activity of chromium-doped bismuth vanadate hollow spheres and achieved a significant improvement in the efficiency and stability of photocatalytic water splitting for hydrogen production.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-18
- Publication Date
- 2026-03-17
AI Technical Summary
Chromium-doped bismuth vanadate hollow spheres exhibit low photocatalytic activity, particularly insufficient reducing power and charge separation efficiency, resulting in low efficiency in photocatalytic water splitting for hydrogen production.
Copper-doped zinc cadmium sulfide nanoparticles were modified on the surface of chromium-doped bismuth vanadate hollow spheres to form a copper-doped zinc cadmium sulfide/chromium-doped bismuth vanadate hollow sphere composite photocatalyst, which improved light absorption capacity and electrical performance through synergistic effect.
It significantly improved the efficiency of photocatalytic water splitting for hydrogen production, achieving a photocatalytic hydrogen production of 49.1 mmol·g⁻¹ within 3 hours, and the material exhibited good cycle stability.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the field of photocatalysis, in particular to a copper-doped zinc cadmium sulfide / chromium-doped bismuth vanadate hollow sphere composite photocatalyst, a preparation method thereof, and application of the photocatalyst in water decomposition for hydrogen production. BACKGROUND
[0002] With the exhaustion of traditional fossil fuels and the increasing development of environment-friendly science and technology, photocatalytic hydrogen production technology has become an important research direction in the field of energy conversion due to its high-density chemical energy, low pollution and renewability. Bismuth vanadate, as a common semiconductor oxide, has excellent photocatalytic stability, and the hollow structure constructed has excellent light absorption capacity. In addition, the doping of chromium effectively inhibits the recombination of electron-hole pairs. However, the chromium-doped bismuth vanadate hollow sphere still has the problem of low reduction capacity, resulting in low photocatalytic activity. Copper-doped zinc cadmium sulfide nanoparticles, as a kind of multi-metal sulfide, can further improve the electrical conductivity of the material by virtue of the synergistic effect between copper-doped zinc cadmium sulfide and chromium-doped bismuth vanadate hollow spheres, and in the catalytic process, the reaction energy barrier is reduced, the reaction adsorption energy is adjusted, and the photocatalytic hydrogen evolution performance is greatly affected.
[0003] Therefore, the copper-doped zinc cadmium sulfide is modified on the surface of the chromium-doped bismuth vanadate hollow sphere to prepare a composite photocatalyst, which can effectively improve the light absorption capacity of the composite, improve the electrical properties, and further improve the efficiency of photocatalytic water decomposition for hydrogen production.
[0004] In view of this, the present application is proposed. SUMMARY
[0005] In order to improve the photocatalytic hydrogen production capacity of the chromium-doped bismuth vanadate hollow sphere and solve the problems of low reduction capacity and low charge separation efficiency, the present application provides a copper-doped zinc cadmium sulfide / chromium-doped bismuth vanadate hollow sphere composite photocatalyst, which is based on the chromium-doped bismuth vanadate hollow sphere and has copper-doped zinc cadmium sulfide nanoparticles modified on the surface of the chromium-doped bismuth vanadate hollow sphere. The present application also provides a preparation method of the copper-doped zinc cadmium sulfide / chromium-doped bismuth vanadate hollow sphere composite photocatalyst and its application in the field of water decomposition for hydrogen production.
[0006] The present application aims to provide a preparation method of the above-mentioned copper-doped zinc cadmium sulfide / chromium-doped bismuth vanadate hollow sphere composite photocatalyst, which specifically comprises the following steps:
[0007] (1) Dissolve zinc acetate and cadmium acetate in deionized water, then add sodium sulfide solution and stir for 2 hours, then add a certain amount of 0.1 mol / L copper nitrate solution to the mixture and continue to stir for 10 minutes, and then transfer the obtained mixture to a stainless steel high-pressure reaction kettle, and react at 160 oC Hydrothermal reaction for 4 hours, after the reaction is completed, the product is cooled to room temperature, and is washed and centrifuged for three times, and is dried in a vacuum drying box for 12 hours at 60 o C Vacuum drying to obtain copper-doped zinc sulfide cadmium;
[0008] (2) Ammonium metavanadate is dissolved in deionized water, stirred at room temperature for 1.5 hours, bismuth nitrate and chromium nitrate are dissolved in a 2 mol / L nitric acid solution, stirred at room temperature for 1.5 hours, then the ammonium metavanadate solution is slowly added to the bismuth nitrate and chromium nitrate solution at a speed of 30 drops per minute, and the pH is adjusted to 7 with a sodium hydroxide solution, and the obtained yellow mixed solution is transferred to a stainless steel high-pressure reaction kettle, reacted at 180°C for 12 hours, the product is filtered, washed with deionized water and ethanol in sequence, and dried to obtain chromium-doped bismuth vanadate hollow spheres;
[0009] (3) The chromium-doped bismuth vanadate hollow spheres are dispersed in 50 mL of copper-doped zinc sulfide cadmium nanoparticle solution, stirred at room temperature for 12 hours, the obtained product is washed with water and ethanol for multiple times, and dried in a vacuum drying box for 12 hours to obtain a copper-doped zinc sulfide cadmium / chromium-doped bismuth vanadate hollow sphere composite photocatalyst.
[0010] Preferably, in the step (1), the molar ratio of zinc acetate and cadmium acetate is 1:(0.6-3).
[0011] Preferably, in the step (1), the volume of copper nitrate solution is 5-20 mL.
[0012] Preferably, in the step (1), the concentration of sodium sulfide solution is 0.3-0.5 mol / L.
[0013] Preferably, in the step (2), the molar ratio of ammonium metavanadate, bismuth nitrate and chromium nitrate is 1:1:0.02-0.1.
[0014] Preferably, in the step (3), the mass ratio of chromium-doped bismuth vanadate hollow spheres and copper-doped zinc sulfide cadmium is 1:0.1-2.
[0015] Another object of the present application is to provide the application of the above-mentioned copper-doped zinc sulfide cadmium / chromium-doped bismuth vanadate hollow sphere composite photocatalyst in photocatalytic hydrogen production. In the photocatalytic hydrogen production test, a 300 W xenon lamp is used as a light source, sodium sulfide and sodium sulfite are used as a sacrificial agent, 10 mg of photocatalyst is added, and a magnetic stirrer is turned on throughout the process to maintain the suspension and dispersion of the catalyst, and a gas chromatograph (GC-2014) is used to determine the hydrogen production.
[0016] Compared with the prior art, the preparation method of the copper-doped cadmium zinc sulfide / chromium-doped bismuth vanadate hollow sphere composite photocatalyst provided by the application is easy to synthesize, and raw materials are widely sourced. The copper-doped cadmium zinc sulfide / chromium-doped bismuth vanadate hollow sphere prepared by using the application as a photocatalyst has a hydrogen production effect that is obviously improved compared with that of the chromium-doped bismuth vanadate hollow sphere, and the amount of hydrogen produced by photocatalysis in 3 hours can reach 49.1 mmol·g -1 Meanwhile, the material has good cycle stability. BRIEF DESCRIPTION OF DRAWINGS
[0017] Figure 1 A scanning electron microscope photo of the copper-doped cadmium zinc sulfide prepared for Example 1.
[0018] Figure 2 A scanning electron microscope photo of the chromium-doped bismuth vanadate hollow sphere prepared for Example 2.
[0019] Figure 3 A scanning electron microscope photo of the copper-doped cadmium zinc sulfide / chromium-doped bismuth vanadate hollow sphere composite photocatalyst prepared for Example 3.
[0020] Figure 4 A photocatalytic hydrogen production graph of the catalyst materials prepared for Examples 1, 2 and 3. DETAILED DESCRIPTION
[0021] The application will be further described below in combination with specific examples:
[0022] Example 1
[0023] The embodiment provides a preparation method of copper-doped cadmium zinc sulfide, comprising the following steps:
[0024] (1) 0.548 g of zinc acetate dihydrate and 0.666 g of cadmium acetate dihydrate are dissolved in 80 mL of deionized water, then 20 mL of a sodium sulfide solution with a concentration of 0.3 mol / L is added, and stirring is performed for 2 hours. Then, 10 mL of a copper nitrate solution with a concentration of 0.1 mol / L is added to the mixed solution, and stirring is continued for 10 minutes. The obtained mixture is transferred to a stainless steel high-pressure reaction kettle, and hydrothermal reaction is performed at 160 °C for 4 hours. After the reaction is completed, the product is cooled to room temperature, and the product is centrifuged, washed and dried three times at 60 o C under vacuum to obtain copper-doped cadmium zinc sulfide.
[0025] Example 2
[0026] The embodiment provides a preparation method of chromium-doped bismuth vanadate hollow spheres, comprising the following steps:
[0027] (2) 5 mmol of ammonium metavanadate was dissolved in 30 mL of deionized water and stirred at room temperature for 1.5 hours, while 5 mmol of bismuth nitrate and 0.2 mmol of chromium nitrate were dissolved in 30 mL of nitric acid solution with a concentration of 2 mol / L and stirred at room temperature for 1.5 hours. Then the ammonium metavanadate solution was slowly added to the bismuth nitrate and chromium nitrate solution at a rate of 30 drops per minute, and the pH was adjusted to 7 with sodium hydroxide solution. The resulting yellow mixture was transferred to a hydrothermal reactor and reacted at 180°C for 12 hours. The product was filtered, washed with deionized water and ethanol in sequence, and dried to obtain chromium-doped bismuth vanadate hollow spheres.
[0028] Example 3
[0029] The present embodiment provides a preparation method of copper-doped zinc cadmium sulfide / chromium-doped bismuth vanadate hollow sphere composite photocatalyst, comprising the following steps:
[0030] (1) 0.548 g of zinc acetate dihydrate and 0.666 g of cadmium acetate dihydrate were dissolved in 80 mL of deionized water, then 20 mL of sodium sulfide solution with a concentration of 0.3 mol / L was added and stirred for 2 hours. Then 10 mL of 0.1 mol / L copper nitrate solution was added to the mixture and stirred for another 10 minutes. The resulting mixture was transferred to a stainless steel high-pressure reactor and hydrothermally reacted at 160°C for 4 hours. After the reaction was completed, it was cooled to room temperature. The product was centrifuged three times, washed, and dried in a vacuum oven at 60°C for 12 hours to obtain copper-doped zinc cadmium sulfide. o C vacuum drying, to obtain copper-doped zinc cadmium sulfide;
[0031] (2) 5 mmol of ammonium metavanadate was dissolved in 30 mL of deionized water and stirred at room temperature for 1.5 hours, while 5 mmol of bismuth nitrate and 0.2 mmol of chromium nitrate were dissolved in 30 mL of nitric acid solution with a concentration of 2 mol / L and stirred at room temperature for 1.5 hours. Then the ammonium metavanadate solution was slowly added to the bismuth nitrate and chromium nitrate solution at a rate of 30 drops per minute, and the pH was adjusted to 7 with sodium hydroxide solution. The resulting yellow mixture was transferred to a hydrothermal reactor and reacted at 180°C for 12 hours. The product was filtered, washed with deionized water and ethanol in sequence, and dried to obtain chromium-doped bismuth vanadate hollow spheres;
[0032] (3) 30 mg of chromium-doped bismuth vanadate hollow spheres were dispersed in 50 mL of a solution containing 30 mg of copper-doped zinc cadmium sulfide nanoparticles and stirred at room temperature for 12 hours. After centrifugation, the resulting product was washed with water and ethanol several times and dried in a vacuum drying oven for 12 hours to obtain a copper-doped zinc cadmium sulfide / chromium-doped bismuth vanadate hollow sphere composite photocatalyst.
[0033] The copper-doped zinc cadmium sulfide prepared in Example 1 was subjected to scanning electron microscope testing, and the test results are shown inFigure 1 As shown in the figure, the copper-doped zinc cadmium sulfide has a quasi-spherical structure.
[0034] The chromium-doped bismuth vanadate hollow sphere prepared in Example 2 was subjected to scanning electron microscope test, and the test results are shown in Figure 2 As shown in the figure, the chromium-doped bismuth vanadate hollow sphere is composed of a large number of nanosheets on the surface.
[0035] The copper-doped zinc cadmium sulfide / chromium-doped bismuth vanadate hollow sphere composite photocatalyst prepared in Example 3 was subjected to scanning electron microscope test, and the test results are shown in Figure 3 As shown in the figure, the chromium-doped bismuth vanadate hollow sphere is coated with a layer of copper-doped zinc cadmium sulfide particles.
[0036] The products obtained in Examples 1, 2 and 3 were subjected to photocatalytic hydrogen production performance test. The specific method is as follows: 100 mL of deionized water, 8.41 g of sodium sulfide, 3.15 g of anhydrous sodium sulfite and 10 mg of photocatalyst were added into a photochemical reactor. Before the test, the closed test system was vacuumed for 30 min using a vacuum pump. In the photocatalytic hydrogen production test, a 300 W xenon lamp was used as the light source, a magnetic stirrer was used to maintain the suspension and dispersion of the catalyst, and a gas chromatograph (GC-2014) was used to determine the hydrogen production, and the results are shown in Figure 4 As shown in the figure:
[0037] 1. When the copper-doped zinc cadmium sulfide prepared in Example 1 is used as a photocatalyst, the photocatalytic hydrogen production within 3 hours is 9.86 mmol·g -1 ;
[0038] 2. When the copper-doped chromium-doped bismuth vanadate hollow sphere prepared in Example 2 is used as a photocatalyst, the photocatalytic hydrogen production within 3 hours is 25 μmol·g -1 ;
[0039] 3. When the copper-doped zinc cadmium sulfide / chromium-doped bismuth vanadate hollow sphere composite photocatalyst prepared in Example 3 is used, the photocatalytic hydrogen production within 3 hours is significantly improved, which can reach 49.1 mmol·g -1 .
[0040] The above experimental results show that after the surface of the chromium-doped bismuth vanadate hollow sphere is modified with copper-doped zinc cadmium sulfide, the photocatalytic hydrogen production is significantly improved, which proves that the composite of copper-doped zinc cadmium sulfide / chromium-doped bismuth vanadate hollow sphere can effectively enhance the photocatalytic hydrogen production performance.
[0041] Example 4
[0042] The present embodiment provides a preparation method of a copper-doped zinc cadmium sulfide / chromium-doped bismuth vanadate hollow sphere composite photocatalyst, which comprises the following steps:
[0043] (1) 0.548 g of zinc acetate dihydrate and 1.998 g of cadmium acetate dihydrate were dissolved in 80 mL of deionized water, followed by the addition of 20 mL of a sodium sulfide solution with a concentration of 0.5 mol / L, and stirring for 2 hours. Then 10 mL of a copper nitrate solution with a concentration of 0.1 mol / L was added to the mixture, and stirring was continued for 10 minutes. The resulting mixture was transferred to a stainless steel high-pressure reaction kettle, and hydrothermal reaction was carried out at 160°C for 4 hours. After the reaction was completed, the product was cooled to room temperature, and was centrifuged, washed, and dried in a vacuum drying oven at 60°C for 12 hours to obtain copper-doped cadmium zinc sulfide. o C vacuum drying, to obtain copper-doped cadmium zinc sulfide;
[0044] (2) 5 mmol of ammonium metavanadate was dissolved in 30 mL of deionized water, and stirring was carried out at room temperature for 1.5 hours. Meanwhile, 5 mmol of bismuth nitrate and 0.2 mmol of chromium nitrate were dissolved in 30 mL of a nitric acid solution with a concentration of 2 mol / L, and stirring was carried out at room temperature for 1.5 hours. Subsequently, the ammonium metavanadate solution was slowly added dropwise to the bismuth nitrate and chromium nitrate solution at a rate of 30 drops per minute, and the pH was adjusted to 7 using a sodium hydroxide solution. The resulting yellow mixture was transferred to a hydrothermal reaction kettle, and reaction was carried out at 180°C for 12 hours. The product was filtered, washed with deionized water and ethanol in sequence, and dried, to obtain chromium-doped bismuth vanadate hollow spheres.
[0045] (3) 30 mg of the chromium-doped bismuth vanadate hollow spheres were dispersed in 50 mL of a solution containing 30 mg of copper-doped cadmium zinc sulfide nanoparticles, and stirring was carried out at room temperature for 12 hours. After centrifugation, the resulting product was washed with water and ethanol multiple times, and was dried in a vacuum drying oven for 12 hours, to obtain a copper-doped cadmium zinc sulfide / chromium-doped bismuth vanadate hollow sphere composite photocatalyst.
[0046] Example 5
[0047] The present embodiment provides a preparation method of a copper-doped cadmium zinc sulfide / chromium-doped bismuth vanadate hollow sphere composite photocatalyst, which comprises the following steps:
[0048] (1) 0.548 g of zinc acetate dihydrate and 1.998 g of cadmium acetate dihydrate were dissolved in 80 mL of deionized water, followed by the addition of 20 mL of a sodium sulfide solution with a concentration of 0.5 mol / L, and stirring for 2 hours. Then 5 mL of a copper nitrate solution with a concentration of 0.1 mol / L was added to the mixture, and stirring was continued for 10 minutes. The resulting mixture was transferred to a stainless steel high-pressure reaction kettle, and hydrothermal reaction was carried out at 160°C for 4 hours. After the reaction was completed, the product was cooled to room temperature, and was centrifuged, washed, and dried in a vacuum drying oven at 60°C for 12 hours to obtain copper-doped cadmium zinc sulfide. o C vacuum drying, to obtain copper-doped cadmium zinc sulfide;
[0049] (2) 5 mmol of ammonium metavanadate was dissolved in 30 mL of deionized water and stirred at room temperature for 1.5 hours. Simultaneously, 5 mmol of bismuth nitrate and 0.2 mmol of chromium nitrate were dissolved in 30 mL of 2 mol / L nitric acid solution and stirred at room temperature for 1.5 hours. Subsequently, the ammonium metavanadate solution was slowly added dropwise to the bismuth nitrate and chromium nitrate solutions at a rate of 30 drops per minute, and the pH was adjusted to 7 with sodium hydroxide solution. The resulting yellow mixture was transferred to a hydrothermal reactor and reacted at 180°C for 12 hours. The product was filtered, washed successively with deionized water and ethanol, and dried to obtain chromium-doped bismuth vanadate hollow spheres.
[0050] (3) 30 mg of chromium-doped bismuth vanadate hollow spheres were dispersed in 50 mL of a solution containing 30 mg of copper-doped zinc cadmium sulfide nanoparticles. The mixture was stirred at room temperature for 12 hours. After centrifugation, the product was washed multiple times with water and ethanol and dried in a vacuum drying oven for 12 hours to obtain a copper-doped zinc cadmium sulfide / chromium-doped bismuth vanadate hollow sphere composite photocatalyst.
[0051] Example 6
[0052] This embodiment provides a method for preparing a copper-doped zinc cadmium sulfide / chromium-doped bismuth vanadate hollow sphere composite photocatalyst, comprising the following steps:
[0053] (1) Dissolve 0.548 g of zinc acetate dihydrate and 0.666 g of cadmium acetate dihydrate in 80 mL of deionized water, then add 20 mL of 0.3 mol / L sodium sulfide solution and stir for 2 hours. Then add 10 mL of 0.1 mol / L copper nitrate solution to the mixture and continue stirring for 10 minutes. Transfer the resulting mixture to a stainless steel high-pressure reactor and hydrothermally react at 160°C for 4 hours. After the reaction, cool to room temperature, and centrifuge and wash the product three times. o Vacuum drying at C yields copper-doped zinc cadmium sulfide.
[0054] (2) 5 mmol of ammonium metavanadate was dissolved in 30 mL of deionized water and stirred at room temperature for 1.5 hours. Simultaneously, 5 mmol of bismuth nitrate and 0.5 mmol of chromium nitrate were dissolved in 30 mL of 2 mol / L nitric acid solution and stirred at room temperature for 1.5 hours. Subsequently, the ammonium metavanadate solution was slowly added dropwise to the bismuth nitrate and chromium nitrate solutions at a rate of 30 drops per minute, and the pH was adjusted to 7 with sodium hydroxide solution. The resulting yellow mixture was transferred to a hydrothermal reactor and reacted at 180°C for 12 hours. The product was filtered, washed successively with deionized water and ethanol, and dried to obtain chromium-doped bismuth vanadate hollow spheres.
[0055] (3) 30 mg of chromium-doped bismuth vanadate hollow spheres were dispersed in 50 mL of a solution containing 30 mg of copper-doped zinc cadmium sulfide nanoparticles. The mixture was stirred at room temperature for 12 hours. After centrifugation, the product was washed multiple times with water and ethanol and dried in a vacuum drying oven for 12 hours to obtain a copper-doped zinc cadmium sulfide / chromium-doped bismuth vanadate hollow sphere composite photocatalyst.
[0056] Example 7
[0057] This embodiment provides a method for preparing a copper-doped zinc cadmium sulfide / chromium-doped bismuth vanadate hollow sphere composite photocatalyst, comprising the following steps:
[0058] (1) Dissolve 0.548 g of zinc acetate dihydrate and 0.666 g of cadmium acetate dihydrate in 80 mL of deionized water, then add 20 mL of 0.3 mol / L sodium sulfide solution and stir for 2 hours. Then add 10 mL of 0.1 mol / L copper nitrate solution to the mixture and continue stirring for 10 minutes. Transfer the resulting mixture to a stainless steel high-pressure reactor and hydrothermally react at 160°C for 4 hours. After the reaction, cool to room temperature, and centrifuge and wash the product three times. o Vacuum drying at C yields copper-doped zinc cadmium sulfide.
[0059] (2) 5 mmol of ammonium metavanadate was dissolved in 30 mL of deionized water and stirred at room temperature for 1.5 hours. Simultaneously, 5 mmol of bismuth nitrate and 0.2 mmol of chromium nitrate were dissolved in 30 mL of 2 mol / L nitric acid solution and stirred at room temperature for 1.5 hours. Subsequently, the ammonium metavanadate solution was slowly added dropwise to the bismuth nitrate and chromium nitrate solutions at a rate of 30 drops per minute, and the pH was adjusted to 7 with sodium hydroxide solution. The resulting yellow mixture was transferred to a hydrothermal reactor and reacted at 180°C for 12 hours. The product was filtered, washed successively with deionized water and ethanol, and dried to obtain chromium-doped bismuth vanadate hollow spheres.
[0060] (3) 30 mg of chromium-doped bismuth vanadate hollow spheres were dispersed in 50 mL of a solution containing 10 mg of copper-doped zinc cadmium sulfide nanoparticles. The mixture was stirred at room temperature for 12 hours. After centrifugation, the product was washed multiple times with water and ethanol and dried in a vacuum drying oven for 12 hours to obtain a copper-doped zinc cadmium sulfide / chromium-doped bismuth vanadate hollow sphere composite photocatalyst.
[0061] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention in any other way. Any person skilled in the art may make changes or modifications to the disclosed technical content to create equivalent embodiments. However, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention are still covered within the protection scope of the present invention.
Claims
1. A method for preparing a copper-doped zinc cadmium sulfide / chromium-doped bismuth vanadate hollow sphere composite photocatalyst, characterized in that, The method comprises the following steps: (1) zinc acetate and cadmium acetate were dissolved in deionized water, then sodium sulfide solution was added, and stirred for 2 hours, then a certain amount of 0.1 mol / L copper nitrate solution was added to the mixture, and stirred for 10 minutes, and the obtained mixture was transferred to a stainless steel high-pressure reaction kettle, and reacted at 160 o C for 4 hours, and after the reaction was completed, it was cooled to room temperature, and the product was centrifuged, washed three times, and dried in a vacuum at 60 o C to obtain copper-doped zinc sulfide cadmium; (2) dissolving ammonium metavanadate in deionized water and stirring for 1.5 hours at room temperature, dissolving bismuth nitrate and chromium nitrate in a nitric acid solution with a concentration of 2 mol / L and stirring for 1.5 hours at room temperature, then slowly adding the ammonium metavanadate solution to the bismuth nitrate and chromium nitrate solution at a rate of 30 drops per minute, adjusting the pH to 7 with a sodium hydroxide solution, transferring the resulting yellow mixture to a stainless steel high-pressure reaction kettle, and reacting for 12 hours at 180°C, and then drying the product after being filtered, washed with deionized water and ethanol in sequence, and dried to obtain chromium-doped bismuth vanadate hollow spheres; (3) dispersing the chromium-doped bismuth vanadate hollow spheres in 50 mL of copper-doped cadmium zinc sulfide nanoparticles solution, stirring for 12 hours at room temperature, washing the resulting product with water and ethanol multiple times after centrifugation, and drying in a vacuum drying oven for 12 hours to obtain a copper-doped cadmium zinc sulfide / chromium-doped bismuth vanadate hollow sphere composite photocatalyst.
2. The method for preparing the copper-doped cadmium zinc sulfide / chromium-doped bismuth vanadate hollow sphere composite photocatalyst according to claim 1, characterized in that, In the step (1), the molar ratio of zinc acetate to cadmium acetate is 1:(0.6-3).
3. The method for preparing the copper-doped cadmium zinc sulfide / chromium-doped bismuth vanadate hollow sphere composite photocatalyst according to claim 1, characterized in that, In the step (1), the volume of copper nitrate solution is 5-20 mL.
4. The method for preparing the copper-doped cadmium zinc sulfide / chromium-doped bismuth vanadate hollow sphere composite photocatalyst according to claim 1, characterized in that, In the step (1), the concentration of sodium sulfide solution is 0.3-0.5 mol / L.
5. The method for preparing the copper-doped cadmium zinc sulfide / chromium-doped bismuth vanadate hollow sphere composite photocatalyst according to claim 1, characterized in that, In the step (2), the molar ratio of ammonium metavanadate, bismuth nitrate, and chromium nitrate is 1:1:0.02-0.
1.
6. The method for preparing the copper-doped cadmium zinc sulfide / chromium-doped bismuth vanadate hollow sphere composite photocatalyst according to claim 1, characterized in that, In the step (3), the mass ratio of chromium-doped bismuth vanadate hollow spheres to copper-doped cadmium zinc sulfide is 1:0.1-2.
7. A hollow sphere composite photocatalyst of copper-doped cadmium zinc sulfide / chromium-doped bismuth vanadate, characterized by, The copper-doped cadmium zinc sulfide / chromium-doped bismuth vanadate hollow sphere composite photocatalyst is prepared by the preparation method of claim 1.