A three-arm type cadmium sulfide nanorod photocatalyst and a preparation method and application thereof
By loading molybdenum disulfide and iridium disulfide cocatalysts onto the tips of three-armed cadmium sulfide nanorods, the problems of photocorrosion and photogenerated carrier recombination were solved, thereby improving the hydrogen production performance and efficiency of the photocatalyst.
Patent Information
- Application Number
- CN202610526157.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-04-21
- Publication Date
- 2026-06-26
AI Technical Summary
Existing cadmium sulfide photocatalysts suffer from low efficiency due to photocorrosion and rapid recombination of photogenerated carriers, and nanorods with single supported cocatalysts do not exhibit ideal hydrogen production performance.
Molybdenum disulfide and iridium disulfide nanoflower-like cocatalysts are loaded onto the three tips of the three-armed cadmium sulfide nanorods. The cocatalysts are efficiently loaded through hydrothermal reaction, which promotes the rapid transfer of photogenerated charge carriers and the efficient separation of electron-hole pairs.
It significantly improved photocatalytic performance, enhanced hydrogen production performance, and enabled rapid transfer of photogenerated carriers and the provision of more active sites.
Smart Images
Figure CN122273594A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of photocatalysis, and particularly relates to a three-armed cadmium sulfide nanorod photocatalyst, its preparation method, and its application. Background Technology
[0002] Cadmium sulfide (CdS) semiconductors are among the most widely studied photocatalysts due to their excellent charge transport properties, low band gap, high electron mobility, and ideal direct band gap. However, problems such as photocorrosion and rapid recombination of photogenerated carriers lead to low photocatalytic efficiency of CdS.
[0003] To address this issue, current methods primarily involve loading other co-catalysts onto cadmium sulfide to create different morphologies, thereby suppressing the recombination of photoexcited charge carriers and ultimately improving the photocatalytic performance of the composite catalyst. However, the hydrogen production performance of cadmium sulfide nanorods obtained by loading a single co-catalyst is not ideal. Summary of the Invention
[0004] Based on the above-mentioned technical problems, this invention achieves efficient separation of photogenerated electron-hole pairs and improves photocatalytic performance by successfully loading molybdenum disulfide and iridium disulfide nanoflower-like cocatalysts onto the tips of three-armed cadmium sulfide nanorods.
[0005] The specific solution of this invention is as follows: This invention provides a three-armed cadmium sulfide nanorod photocatalyst, which comprises: three-armed cadmium sulfide nanorods, molybdenum disulfide, and iridium disulfide; wherein, the three tips of the three-armed cadmium sulfide nanorods are all loaded with molybdenum disulfide and iridium disulfide.
[0006] Preferably, both molybdenum disulfide and iridium disulfide are nanoflower-shaped.
[0007] Preferably, molybdenum disulfide accounts for 5-25% of the total mass of the three-armed cadmium sulfide nanorod photocatalyst; iridium disulfide accounts for 1-5% of the total mass of the three-armed cadmium sulfide nanorod photocatalyst.
[0008] The present invention also provides a method for preparing a three-armed cadmium sulfide nanorod photocatalyst, comprising the following steps: mixing three-armed cadmium sulfide nanorods with iridium chloride and sodium molybdate in a solvent, and obtaining the catalyst through a hydrothermal reaction; wherein the solvent is a mixed solvent of diethylenetriamine and water.
[0009] Preferably, the hydrothermal reaction temperature is 100~180℃ and the hydrothermal reaction time is 12~28h.
[0010] Preferably, the three-armed cadmium sulfide nanorods are mixed with iridium chloride and sodium molybdate in a solvent under stirring and ultrasonic conditions; specifically, the mixture is stirred at 20~50℃ for 1~2h and then ultrasonicated for 0.5~2h.
[0011] Preferably, the mixed solution after the hydrothermal reaction is cooled to room temperature and the precipitate is separated; then the precipitate is washed with water and ethanol and dried to obtain a three-armed cadmium sulfide nanorod photocatalyst.
[0012] Preferably, the preparation method of the three-armed cadmium sulfide nanorods is as follows: cadmium acetate dihydrate and thioacetamide are added sequentially to a mixed solvent of ethylenediamine and water, and the three-armed cadmium sulfide nanorods are obtained by hydrothermal reaction; more preferably, the hydrothermal reaction temperature for preparing the three-armed cadmium sulfide is 120~180℃, and the hydrothermal reaction time is 10~24h.
[0013] Preferably, the mass ratio of ethylenediamine to water is 1.5~2.0:1; the mass ratio of cadmium acetate dihydrate to thioacetamide is 1.5~2.0:1.
[0014] Preferably, in a mixed solvent of ethylenediamine and water, cadmium acetate dihydrate is first added and stirred for 0.5 to 1 hour at 20 to 50°C, followed by the addition of thioacetamide and stirring for another 0.5 to 1 hour. After hydrothermal reaction, the mixture is cooled, centrifuged, and dried to obtain three-armed cadmium sulfide nanorods.
[0015] The present invention also provides the application of the three-armed cadmium sulfide nanorod photocatalyst in photocatalytic hydrogen production.
[0016] The beneficial effects of this invention are: This invention provides a three-armed cadmium sulfide nanorod photocatalyst. Molybdenum disulfide and iridium disulfide are used as cocatalysts to load and modify the three tips of the three-armed cadmium sulfide nanorods, which promotes the rapid transfer of photogenerated carriers, provides more active sites, realizes efficient spatial separation of electron-hole pairs, and significantly improves photocatalytic performance. Compared with cadmium sulfide nanorods with a single supported cocatalyst, the hydrogen production performance is significantly improved.
[0017] This invention also provides a strategy for synthesizing three-terminal uniformly supported co-catalysts, which utilizes IrS2 as the nucleation center of MoS2 and takes advantage of Ir... 3+ The catalyst exhibits similar affinity characteristics for the Cd or S ends of the CdS crystal facet, overcoming the bottleneck of only achieving single-end growth in direct MoS2 growth and successfully realizing symmetrical loading of MoS2 cocatalysts at all three ends. Among these, iridium chloride plays a decisive role in modifying the three ends of the three-armed cadmium sulfide, while sodium molybdate has a significant impact on improving the photocatalytic performance of cadmium sulfide. Attached Figure Description
[0018] Figure 1 The images are scanning electron microscope (SEM) images corresponding to Example 1; where 1(a) is a scanning electron microscope (SEM) image of the three-armed cadmium sulfide nanorods; and 1(b) is a scanning electron microscope (SEM) image of the three-armed cadmium sulfide nanorod photocatalyst. Figure 2Scanning electron microscope image of Cd / MoS2 prepared for Comparative Example 1; Figure 3 Transmission electron microscopy (TEM) image of the three-armed cadmium sulfide nanorod photocatalyst prepared in Example 1. Figure 4 The X-ray photoelectron spectrum of the three-armed cadmium sulfide nanorod photocatalyst material prepared in Example 1 is shown below. Figure 5 Comparison chart of hydrogen production performance of CdS, Cd / MoS2 / IrS2 prepared in Example 1, Cd / MoS2 prepared in Comparative Example 1, and Cd / IrS2 prepared in Comparative Example 2. Detailed Implementation
[0019] The technical solution of the present invention will be described in detail below through specific embodiments. However, it should be clearly stated that these embodiments are for illustrative purposes only and are not intended to limit the scope of the present invention.
[0020] Example 1
[0021] A three-armed cadmium sulfide nanorod photocatalyst comprises: three-armed cadmium sulfide nanorods, molybdenum disulfide, and iridium disulfide; wherein, each of the three tips of the three-armed cadmium sulfide nanorods is loaded with molybdenum disulfide and iridium disulfide; the molybdenum disulfide and iridium disulfide are arranged in a nanoflower-like structure. Molybdenum disulfide accounts for 10% of the total mass of the three-armed cadmium sulfide nanorod photocatalyst; iridium disulfide accounts for 5% of the total mass of the three-armed cadmium sulfide nanorod photocatalyst.
[0022] Its preparation method is as follows: S1. Preparation of three-armed cadmium sulfide nanorods First, weigh out cadmium acetate dihydrate powder and thioacetamide powder separately, making their mass ratio 2:1. At 25°C, add cadmium acetate dihydrate to a mixed solution of ethylenediamine and water (mass ratio 2:1) and stir for 0.5 h, then add thioacetamide and stir for 1 h. Pour the mixed solution into a reaction vessel and heat at 180°C for 24 h. Then, allow it to cool naturally to room temperature, centrifuge, and dry at 60°C to obtain three-armed cadmium sulfide nanorods (denoted as CdS). S2. Preparation of three-armed cadmium sulfide nanorod photocatalysts 150 mg of the above-mentioned three-armed cadmium sulfide nanorods were dispersed in a mixed solvent of diethylenetriamine and water. Subsequently, 20 mg of sodium molybdate and 10 mg of iridium chloride powder were added to the mixed solution, and the mixture was stirred at 25 °C for 1 hour and sonicated for 30 minutes. The mixed solution was then poured into a reaction vessel and heated at 180 °C for 16 h. After naturally cooling to room temperature, the precipitate was obtained by centrifugation and washed 6 times with deionized water and ethanol. Finally, the precipitate was dried at 60 °C to obtain the three-armed cadmium sulfide nanorod photocatalyst (denoted as Cd / MoS2 / IrS2).
[0023] The scanning electron microscope image of the three-armed cadmium sulfide nanorods prepared in Example S1 is shown below. Figure 1 As shown in (a); the scanning electron microscope image of the three-armed cadmium sulfide nanorod photocatalyst prepared by S2 is shown in Figure 1. Figure 1 As shown in (b), it can be seen that nanoflower-like cocatalysts are grown at all three ends of the three-armed cadmium sulfide nanorods obtained in S1.
[0024] The transmission electron microscope image of the three-armed cadmium sulfide nanorod photocatalyst prepared in Example S2 is shown below. Figure 3 As shown, both molybdenum disulfide and iridium disulfide, the two co-catalysts, are supported on the tips of the three-armed cadmium sulfide.
[0025] The X-ray photoelectron spectrum of the three-armed cadmium sulfide nanorod photocatalyst prepared in Example S2 is as follows: Figure 4 As shown, the interatomic interactions demonstrate the successful loading of the co-catalysts molybdenum disulfide and iridium disulfide.
[0026] Example 2 A three-armed cadmium sulfide nanorod photocatalyst comprises: three-armed cadmium sulfide nanorods, molybdenum disulfide, and iridium disulfide; wherein each of the three tips of the three-armed cadmium sulfide nanorods is loaded with molybdenum disulfide and iridium disulfide; the molybdenum disulfide and iridium disulfide are arranged in a nanoflower-like structure. Molybdenum disulfide accounts for 20% of the total mass of the three-armed cadmium sulfide nanorod photocatalyst; iridium disulfide accounts for 5% of the total mass of the three-armed cadmium sulfide nanorod photocatalyst.
[0027] Its preparation method is as follows: S1. Preparation of three-armed cadmium sulfide nanorods, the same as in Example 1; S2. Preparation of three-armed cadmium sulfide nanorod photocatalysts 150 mg of the aforementioned three-armed cadmium sulfide nanorods were dispersed in a mixed solvent of diethylenetriamine and water. Subsequently, 40 mg of sodium molybdate and 10 mg of iridium chloride powder were added to the mixed solution, and the mixture was stirred at 25 °C for 1 hour and sonicated for 30 minutes. The mixed solution was then poured into a reaction vessel and heated at 180 °C for 16 hours. After naturally cooling to room temperature, the precipitate was obtained by centrifugation and washed 3-6 times with deionized water and ethanol. Finally, the precipitate was dried at 60 °C to obtain the three-armed cadmium sulfide nanorod photocatalyst.
[0028] Comparative Example 1 A three-armed molybdenum disulfide-modified cadmium sulfide nanorod, the preparation method of which includes:
[0029] S1. Preparation of three-armed cadmium sulfide nanorods, the same as in Example 1; S2. 150 mg of the three-armed cadmium sulfide nanorods obtained in S1 were dispersed in a mixed solution of diethylenetriamine and water. Subsequently, 20 mg of sodium molybdate powder was added to the mixed solution, and the mixture was stirred at 25 °C for 1 hour and sonicated for 30 minutes. The mixed solution was then poured into a reaction vessel and heated at 180 °C for 16 h. After naturally cooling to room temperature, the precipitate was obtained by centrifugation and washed 6 times with deionized water and ethanol. Finally, the precipitate was dried at 60 °C to obtain three-armed molybdenum disulfide modified cadmium sulfide nanorods (denoted as Cd / MoS2).
[0030] The SEM image of the three-armed molybdenum disulfide modified cadmium sulfide nanorods obtained in this comparative example is shown below. Figure 2 As shown in the figure, it can be seen that only single-end growth can be achieved when MoS2 is grown directly.
[0031] Comparative Example 2 A three-armed iridium disulfide-modified cadmium sulfide nanorod, the preparation method of which includes: S1. Preparation of three-armed cadmium sulfide nanorods, the same as in Example 1; S2. 150 mg of the three-armed cadmium sulfide nanorods obtained in S1 were dispersed in a mixed solution of diethylenetriamine and water. Subsequently, 10 mg of iridium chloride powder was added to the mixed solution, and the mixture was stirred at 25 °C for 1 hour and sonicated for 30 minutes. The mixed solution was then poured into a reaction vessel and heated at 180 °C for 16 hours. After naturally cooling to room temperature, the precipitate was obtained by centrifugation and washed 6 times with deionized water and ethanol. Finally, the precipitate was dried at 60 °C to obtain three-armed iridium disulfide modified cadmium sulfide nanorods (denoted as Cd / IrS2).
[0032] The catalytic hydrogen production performance of the three-armed cadmium sulfide nanorods CdS, the three-armed cadmium sulfide nanorod photocatalyst Cd / MoS2 / IrS2 obtained in Example 1, and the photocatalysts Cd / MoS2 and Cd / IrS2 described in Comparative Examples 1 and 2 were tested. The test methods and results are shown below: A 300 W xenon lamp (equipped with a 420 nm filter, luminous intensity 470 mW cm⁻¹) was used. -2 Using a light source, the hydrogen production performance of samples from Example 1, Comparative Examples 1 and 2 was investigated in a 50 mL round-bottom flask. The specific procedure was as follows: 5 mg of catalyst was weighed and placed in 20 mL of Na2S / Na2SO3 aqueous solution. After sealing, Ar gas was passed through to remove residual oxygen for about 15 min. The hydrogen produced during the illumination process was sampled and analyzed in real time using an SP-6590 gas chromatograph.
[0033] Test results are as follows Figure 5As shown, the three-armed cadmium sulfide nanorod CdS photocatalyst obtained in Example 1 has significantly improved hydrogen production performance compared to the three-armed cadmium sulfide nanorod CdS obtained in step S1 of Example 1, and the photocatalysts Cd / MoS2 and Cd / IrS2 described in Comparative Examples 1 and 2.
[0034] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.
Claims
1. A three-armed cadmium sulfide nanorod photocatalyst, characterized in that, Its composition includes: three-armed cadmium sulfide nanorods, molybdenum disulfide, and iridium disulfide; wherein, the three tips of the three-armed cadmium sulfide nanorods are all loaded with molybdenum disulfide and iridium disulfide.
2. The three-armed cadmium sulfide nanorod photocatalyst according to claim 1, characterized in that, Both molybdenum disulfide and iridium disulfide are nanoflower-like.
3. The three-armed cadmium sulfide nanorod photocatalyst according to claim 1 or 2, characterized in that, Molybdenum disulfide accounts for 5-25% of the total mass of the three-armed cadmium sulfide nanorod photocatalyst; iridium disulfide accounts for 1-5% of the total mass of the three-armed cadmium sulfide nanorod photocatalyst.
4. The method for preparing the three-armed cadmium sulfide nanorod photocatalyst according to any one of claims 1-3, characterized in that, The process includes the following steps: mixing three-armed cadmium sulfide nanorods with iridium chloride and sodium molybdate in a solvent, followed by a hydrothermal reaction; the solvent is a mixture of diethylenetriamine and water.
5. The method for preparing the three-armed cadmium sulfide nanorod photocatalyst according to claim 4, characterized in that, The hydrothermal reaction temperature is 100~180℃, and the hydrothermal reaction time is 12~28h.
6. The method for preparing the three-armed cadmium sulfide nanorod photocatalyst according to claim 4 or 5, characterized in that, Three-armed cadmium sulfide nanorods were mixed with iridium chloride and sodium molybdate in a solvent under stirring and sonication conditions; specifically, the mixture was stirred at 20-50°C for 1-2 hours and then sonicated for 0.5-2 hours.
7. The method for preparing the three-armed cadmium sulfide nanorod photocatalyst according to claim 4, characterized in that, The preparation method of three-armed cadmium sulfide nanorods is as follows: cadmium acetate dihydrate and thioacetamide are added sequentially to a mixed solvent of ethylenediamine and water, and three-armed cadmium sulfide nanorods are obtained by hydrothermal reaction; preferably, the hydrothermal reaction temperature for preparing three-armed cadmium sulfide is 120~180℃, and the hydrothermal reaction time is 10~24h.
8. The method for preparing the three-armed cadmium sulfide nanorod photocatalyst according to claim 7, characterized in that, The mass ratio of ethylenediamine to water is 1.5~2.0:1; the mass ratio of cadmium acetate dihydrate to thioacetamide is 1.5~2.0:
1.
9. The method for preparing the three-armed cadmium sulfide nanorod photocatalyst according to claim 7, characterized in that, In a mixed solvent of ethylenediamine and water, cadmium acetate dihydrate was first added and stirred for 0.5 to 1 hour at 20 to 50 °C, followed by the addition of thioacetamide and stirring for another 0.5 to 1 hour. After the hydrothermal reaction, the mixture was cooled, centrifuged, and dried to obtain three-armed cadmium sulfide nanorods.
10. The application of the three-armed cadmium sulfide nanorod photocatalyst according to any one of claims 1-3 or the three-armed cadmium sulfide nanorod photocatalyst prepared by any one of claims 4-9 in photocatalytic hydrogen production.