Application of ZIS / PDA photocatalytic material with photo-thermal synergistic effect
By constructing a Zn2In2S5/PDA composite material, the photoresponse range was broadened and a photothermal synergistic effect was introduced, which solved the problems of narrow photoresponse of Zn2In2S5 and easy recombination of photogenerated carriers, and achieved the effect of efficient production of hydrogen peroxide.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- 高智
- Filing Date
- 2026-03-24
- Publication Date
- 2026-05-12
AI Technical Summary
The existing photocatalyst Zn2In2S5 has a narrow photoresponse range and its photogenerated carriers are prone to recombination, which limits its practical application in the photocatalytic production of hydrogen peroxide.
By constructing a pn junction with polydopamine (PDA), a Zn2In2S5/PDA composite material is formed, which broadens the photoresponse range and promotes charge separation, introducing a photothermal synergistic effect to improve catalytic efficiency.
It significantly improves the quantum efficiency and catalytic activity of photocatalysts, achieves full-spectrum utilization, and enhances the production efficiency and stability of hydrogen peroxide.
Smart Images
Figure CN122010054A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of hydrogen peroxide production technology, and in particular to the application of a Zn2In2S5 / PDA photocatalytic material with photothermal synergistic effect. Background Technology
[0002] Hydrogen peroxide (H2O2), as a green oxidant and clean liquid fuel, is widely used in various industrial and medical fields. Various methods are used to prepare H2O2, including the anthraquinone process, H2O2 catalytic combination method, electrocatalytic O2 reduction method, and electrocatalytic oxidation of H2O2. However, these methods often face limitations hindering their practical application. For example, the anthraquinone process is complex, cumbersome to operate, and carries the risk of organic leakage and serious environmental pollution. The H2O2 catalytic combination method has low efficiency and potential explosion hazards, raising safety concerns. Electrocatalytic synthesis requires additional electrical energy to drive the reaction, increasing overall energy consumption and cost. Therefore, there is a growing need to explore energy-saving and environmentally friendly H2O2 production technologies to meet diverse utilization requirements.
[0003] Photocatalysis has become a promising process for producing H2O2. This process utilizes solar energy to synthesize H2O2 from abundant resources such as H2O and O2, providing a sustainable and green method. Unlike other methods mentioned above, this process uses only sunlight as an energy source, providing mild reaction conditions, simple and controllable operation, and no secondary pollution. Therefore, the selection of photocatalysts is a crucial aspect of photocatalysis technology. Among them, Zn2In2S5 is widely used in the field of photocatalysis due to its favorable electronic properties, band gap and band edge, and tunable optical properties. For a long time, photocatalysis and thermocatalysis have been considered two independent systems. However, photothermal catalysis can simultaneously leverage the advantages of both thermal and photocatalysis. It exhibits good catalytic activity under mild conditions, accelerating the transport of photogenerated charges and the diffusion of products during the reaction. In the photothermal catalysis process, light can trigger chemical reactions, accumulating heat on the material surface and reducing heat input; during the reaction, heat accelerates the reaction, increasing the mobility of photogenerated carriers or the selectivity of reaction products.
[0004] However, the development of Zn₂In₂S₅ in practical photocatalytic applications is still somewhat limited due to its narrow photoresponse range and the ease with which photogenerated carriers recombine. Polydopamine (PDA), as an organic photothermal material, possesses strong light absorption capabilities across the entire wavelength spectrum and can itself act as a p-type semiconductor to construct pn junctions with Zn₂In₂S₅, promoting spatial separation of carriers. Therefore, developing a Zn₂In₂S₅ / PDA photocatalytic material with photothermal effects for the efficient synthesis of H₂O₂ has significant application value. Summary of the Invention
[0005] To address the aforementioned problems in existing technologies, this invention provides an application of the Zn2In2S5 / PDA photocatalytic material. The Zn2In2S5 / PDA composite material prepared by this invention has the advantages of strong photocatalytic activity and good stability, and has broad application prospects in the field of hydrogen peroxide production.
[0006] The technical solution of the present invention is as follows: An application of a ZIS / PDA photocatalytic material for the photocatalytic production of H2O2, wherein the photocatalytic material achieves a catalytic rate of up to 9180 μM∙h during the catalytic process. -1 ∙g -1 ; The ZIS / PDA photocatalytic material is a Zn2In2S5 / PDA composite material, and its preparation method includes the following steps: A. ZnCl2, InCl3, and TAA were dissolved in a mixed solution of deionized water and ethanol at room temperature. The solution was then transferred to a polytetrafluoroethylene liner for hydrothermal reaction. Finally, the solution was washed three times with deionized water and dried in a vacuum drying oven to obtain Zn2In2S5 nanoflowers.
[0007] B. First, prepare a mixed solution of deionized water and ethanol in a volume ratio of 1:1. Weigh a certain mass of Zn₂In₂S₅ and add it to the mixed solution, then sonicate until dispersed. Next, add ammonia to the mixed solution to make the pH 8.5. Weigh different masses of dopamine hydrochloride and add them to the above solution, then stir. Finally, wash three times with deionized water and dry in a vacuum drying oven to obtain Zn₂In₂S₅ / PDA nanoparticles.
[0008] As a further improvement of the present invention, in step A, the molar ratio of ZnCl2, InCl3, and TAA is 2:2:5.
[0009] As a further improvement of the present invention, in step A, the hydrothermal reaction is carried out at 160°C. o Store at C for 12 hours.
[0010] As a further improvement of the present invention, in step B, the mass ratio of Zn₂In₂S₅ to PDA is 1:0.1-0.4. As a further improvement of the present invention, in step B, the stirring temperature is room temperature and the stirring time is 24 h.
[0011] The beneficial technical effects of this invention are as follows: 1. An effective heterostructure was constructed, significantly promoting charge separation: This invention successfully composited polydopamine (PDA) onto the surface of Zn2In2S5 nanoflowers via in-situ self-polymerization, constructing a Zn2In2S5 / PDA composite material with a pn-type heterojunction. This closely contacted heterostructure provides a rapid channel for the migration of photogenerated charge carriers, enabling ultrafast charge transport from semiconductor to polymer and effectively suppressing the recombination of photogenerated electron-hole pairs, thereby significantly improving quantum efficiency.
[0012] 2. Expanded photoresponse range, enabling full-spectrum utilization: The introduction of PDA significantly broadens the light absorption range of Zn2In2S5, extending it from the ultraviolet region to the visible and even near-infrared regions, endowing the material with full-spectrum photocatalytic activity. This characteristic allows the composite material to make fuller use of solar energy, laying the energy foundation for the efficient production of H2O2.
[0013] 3. Introducing a photothermal synergistic effect to optimize reaction kinetics: PDA, as an excellent photothermal material, can effectively increase the microscopic local temperature of the catalyst surface through the photothermal effect generated under illumination. This accelerates reactant diffusion and surface reaction kinetics; on the other hand, the injection of thermal energy further promotes carrier transport efficiency, forming a synergistic effect with the charge separation effect of the heterojunction, jointly improving catalytic efficiency. Attached Figure Description
[0014] Figure 1 SEM images of different photocatalytic materials; Figure 2 FTIR scan results for different photocatalytic materials; Figure 3 The results of ultraviolet diffuse reflectance spectroscopy tests for different photocatalytic materials; Figure 4 To assess the H2O2 generation performance of different photocatalytic materials; Figure 5 The graph shows the temperature rise curves of different photocatalytic materials under illumination. Detailed Implementation
[0015] The present invention will now be described in detail with reference to the accompanying drawings and embodiments. Obviously, the described embodiments are merely some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.
[0016] Example 1: Preparation of Zn2In2S5 / PDA photocatalytic material At room temperature, 2 mmol ZnCl2, 2 mmol InCl3, and 5 mmol TAA were dissolved in a mixture of 30 ml deionized water and 30 ml ethanol. The mixture was then transferred to a 100 ml polytetrafluoroethylene liner for hydrothermal reaction at 160°C. o Store at C for 12 hours. Finally, wash three times with deionized water and dry in a vacuum drying oven at 60°C. o C was dried to obtain Zn2In2S5 nanoflowers.
[0017] First, prepare a 100 ml mixture of deionized water and ethanol (volume ratio 1:1). Weigh 100 mg of Zn₂In₂S₅ and add it to the mixture, then sonicate until dispersed. Next, add 5 ml of ammonia to adjust the pH to 8.5. Weigh 30 mg of dopamine hydrochloride and add it to the solution, then stir at room temperature for 24 h. Finally, wash three times with deionized water and dry in a vacuum oven at 60°C. o Drying at C yielded Zn₂In₂S₅ / 30 wt% PDA nanoparticles, labeled ZP. 0.3 .
[0018] Figure 1 This is a SEM image of the Zn2In2S5 / PDA prepared in Example 1 of this invention. Figure 1 The shape and size of the material are shown. After successful composite, the Zn2In2S5 / PDA photocatalyst is loaded onto Zn2In2S5 nanoflowers by bulk PDA in a bulk island distribution.
[0019] Comparative Example 1 To prepare the photocatalyst Zn₂In₂S₅ alone: 2 mmol ZnCl₂, 2 mmol InCl₃, and 5 mmol TAA were dissolved in a mixture of 30 ml deionized water and 30 ml ethanol at room temperature. The mixture was then transferred to a 100 ml polytetrafluoroethylene liner for hydrothermal reaction at 160°C. o Store at C for 12 hours. Finally, wash three times with deionized water and dry in a vacuum drying oven at 60°C. o C was dried to obtain Zn2In2S5 nanoflowers.
[0020] Comparative Example 2 Preparation of PDA material only: First, prepare a 100 ml mixture of deionized water and ethanol (volume ratio 1:1). Then, weigh out tris(hydroxymethyl)aminomethane and add it to the mixture, stirring thoroughly to obtain a 10 mM Tris buffer solution. Adjust the pH of the solution to 8.5. Next, dissolve dopamine hydrochloride in the above mixture and stir at room temperature for 24 hours. Wash three times with deionized water and dry in a vacuum oven at 60°C. o PDA nanoparticles were obtained by drying C.
[0021] Figure 2 The images show the FT-IR spectra of Zn₂In₂S₅, PDA, and Zn₂In₂S₅ / PDA prepared in Example 1 and Comparative Examples 1 and 2. The peak of polydopamine is located at 1281 cm⁻¹. -1 , corresponding to the stretching vibration of the catechol group; located at 1615 cm. -1 The bands are attributed to the stretching vibration mode of the C=C bond in the aromatic ring of indolequinone; furthermore, at 3200 cm⁻¹... -1 Up to 3600 cm -1 The broad peaks observed between them are related to the −OH and −NH2 groups in the indole structure; Zn2In2S5 / PDA at 1615.8 cm⁻¹ -1 and 1281 cm -1 The appearance of an enhanced peak indicates the presence of indolequinone and catechol structures, thus confirming the successful loading of polydopamine. Example
[0022] Preparation of Zn2In2S5 / PDA photocatalytic materials Zn₂In₂S₅ nanoflower structures were prepared using a solvothermal method. At room temperature, 2 mmol ZnCl₂, 2 mmol InCl₃, and 5 mmol TAA were dissolved in a mixture of 30 ml deionized water and 30 ml ethanol. The solution was then transferred to a 100 ml polytetrafluoroethylene liner for hydrothermal reaction at 160°C. o Store at C for 12 hours. Finally, wash three times with deionized water and dry in a vacuum drying oven at 60°C. o C was dried to obtain Zn2In2S5 nanoflowers.
[0023] First, prepare a 100 ml mixture of deionized water and ethanol (volume ratio 1:1). Weigh 100 mg of Zn₂In₂S₅ and add it to the mixture, then sonicate until dispersed. Next, add 5 ml of ammonia to adjust the pH to 8.5. Weigh 10 mg of dopamine hydrochloride and add it to the solution, then stir at room temperature for 24 h. Finally, wash three times with deionized water and dry in a vacuum oven at 60°C. o Drying at C yielded Zn₂In₂S₅ / 10 wt% PDA nanoparticles, labeled ZP. 0.1 . Example
[0024] Preparation of Zn2In2S5 / PDA photocatalytic materials Zn₂In₂S₅ nanoflower structures were prepared using a solvothermal method. At room temperature, 2 mmol ZnCl₂, 2 mmol InCl₃, and 5 mmol TAA were dissolved in a mixture of 30 ml deionized water and 30 ml ethanol. The solution was then transferred to a 100 ml polytetrafluoroethylene liner for hydrothermal reaction at 160°C. o Store at C for 12 hours. Finally, wash three times with deionized water and dry in a vacuum drying oven at 60°C. o C was dried to obtain Zn2In2S5 nanoflowers.
[0025] B. First, prepare a 100 ml mixture of deionized water and ethanol (volume ratio 1:1). Weigh 100 mg of Zn₂In₂S₅ and add it to the mixture, then sonicate until dispersed. Next, add 5 ml of ammonia to adjust the pH to 8.5. Weigh 20 mg of dopamine hydrochloride and add it to the solution, then stir at room temperature for 24 h. Finally, wash three times with deionized water and dry in a vacuum oven at 60°C. o Drying at C yielded Zn₂In₂S₅ / 20 wt% PDA nanoparticles, labeled ZP. 0.2 . Example
[0026] Preparation of Zn2In2S5 / PDA photocatalytic materials A. Zn₂In₂S₅ nanoflower structures were prepared using a solvothermal method. At room temperature, 2 mmol ZnCl₂, 2 mmol InCl₃, and 5 mmol TAA were dissolved in a mixed solution of 30 ml deionized water and 30 ml ethanol. The solution was then transferred to a 100 ml polytetrafluoroethylene liner for hydrothermal reaction at 160°C. o Store at C for 12 hours. Finally, wash three times with deionized water and dry in a vacuum drying oven at 60°C. o C was dried to obtain Zn2In2S5 nanoflowers.
[0027] B. First, prepare a 100 ml mixture of deionized water and ethanol (volume ratio 1:1). Weigh 100 mg of Zn₂In₂S₅ and add it to the mixture, then sonicate until dispersed. Next, add 5 ml of ammonia to adjust the pH to 8.5. Weigh 40 mg of dopamine hydrochloride and add it to the solution, then stir at room temperature for 24 h. Finally, wash three times with deionized water and dry in a vacuum oven at 60°C. o Drying at C yielded Zn₂In₂S₅ / 40 wt% PDA nanoparticles, labeled ZP. 0.4 .
[0028] Figure 3The UV diffuse reflectance spectra of Zn₂In₂S₅, PDA, and Zn₂In₂S₅ / PDA prepared in Examples 1, 2, 3, 4, and Comparative Examples 1 and 2 are shown. It can be observed that Zn₂In₂S₅ exhibits strong absorption for light with wavelengths between 350-450 nm, while its absorption for wavelengths greater than 450 nm decreases significantly. In contrast, PDA exhibits strong light absorption across the entire spectrum. Furthermore, the light absorption of the Zn₂In₂S₅ / PDA composite material is significantly improved compared to Zn₂In₂S₅ alone across the entire spectrum, and its light absorption increases with increasing PDA content. This indicates that the introduction of PDA can enhance the photoresponse range of Zn₂In₂S₅ alone, enabling the composite material to utilize light energy more efficiently.
[0029] Photocatalytic activity evaluation: The photocatalytic H2O2 production experiments of the photocatalysts Zn2In2S5, PDA, and Zn2In2S5 / PDA prepared in Examples 1, 2, 3, 4 and Comparative Examples 1 and 2 were conducted using the following methods: Material preparation stage: In a three-necked round-bottom flask, weigh out 45 mL of deionized water and 5 mL of isopropanol to form a transparent IPA mixture. Then add 10 mg of catalyst to the IPA solution and perform ultrasonic dispersion until the solute is completely dispersed. Saturated gas environment stage: The mixture in the three-necked round-bottom flask was subjected to uniform oxygen flow for 1 h in the dark, with the flow rate controlled within the range of 150-200 mL / min. ‒1 Continue until the amount of oxygen in the dispersion reaches saturation. Illumination stage: The sealed three-necked round-bottom flask containing the saturated dispersion was transferred to a 300 W xenon lamp. The photocatalytic performance was tested under the light source device with a distance of about 30 cm between the light source and the liquid surface. During the test, 4 mL of suspension was extracted every 20 min. After centrifugation at 10000 rpm for 10 min, 2 mL of supernatant was collected for concentration testing. H2O2 performance evaluation stage: Iodometric determination was performed, by adding 1 mL of 0.1 M C8H5O4K solution and 1 mL of 0.4 MKI solution to 2.0 mL of the supernatant, and then allowing it to stand in the dark for 30 min. This step is based on the fact that the reaction will generate I3. ‒ It exhibits a distinct characteristic adsorption signal around 350 nm. This paper describes the measurement of I3 at 350 nm using UV-Vis spectroscopy. ‒ The absorbance was used to evaluate and determine the H2O2 generation concentration of the catalyst material.
[0030] Figure 4 The chart shows a comparison of the photocatalytic H2O2 production performance of Zn2In2S5, PDA, and Zn2In2S5 / PDA prepared in Example 1 and Comparative Examples 1 and 2. Under the full spectrum, the catalytic performance of the Zn2In2S5 / PDA composite material is significantly improved. With increasing PDA content, the photocatalytic H2O2 production performance of the Zn2In2S5 / PDA composite material first increases and then decreases, with Zn2In2S5 / 30 wt% PDA exhibiting excellent photocatalytic performance. It produced 207.63 μM within 120 min, which is 2.37 times that of Zn2In2S5 (87.69 μM) under the same conditions. Furthermore, the decreased photocatalytic activity of the Zn2In2S5 / 40 wt% PDA composite material may be due to excessive PDA covering the active sites on the Zn2In2S5 surface, thus reducing the material activity.
[0031] Figure 5 This graph shows the temperature changes of different photocatalysts under illumination. Under full-spectrum illumination, the temperature of single Zn₂In₂S₅ after 5 minutes of irradiation is 39.7°C. o C; The surface temperature of the PDA is 72.5°C. o C, which fully demonstrates its potential as a photothermal material; compared with pure Zn2In2S5, the surface temperature of Zn2In2S5 / PDA composite materials is significantly increased. From this, we can see that as the PDA content increases, the surface temperature of Zn2In2S5 / PDA gradually rises; among which ZP 0.4 The temperature reached a maximum of 73.7 degrees Celsius. o The difference between C and Zn2In2S5 is 34. o C.
Claims
1. The application of a Zn₂In₂S₅ / PDA photocatalytic material with photothermal synergistic effect, characterized in that, The Zn2In2S5 / PDA composite material was used as a photocatalyst for the photocatalytic production of hydrogen peroxide (H2O2). The photocatalytic rate of the material in the photocatalytic production of H2O2 reached 9180 μM·h. -1 ·g -1 above.
2. The application according to claim 1, characterized in that, The Zn2In2S5 / PDA composite material is prepared by a method comprising the following steps: A. By mixing zinc source, indium source and sulfur source and carrying out hydrothermal reaction, Zn2In2S5 nanomaterials were prepared. B. Disperse the Zn2In2S5 nanomaterials obtained in step A in a solvent, adjust the pH to alkaline, add dopamine hydrochloride, carry out in-situ polymerization, and dry after solid-liquid separation to obtain Zn2In2S5 / PDA composite material.
3. The application according to claim 2, characterized in that, In step A, the zinc source is ZnCl2, the indium source is InCl3, and the sulfur source is thioacetamide (TAA); the molar ratio of ZnCl2, InCl3, and TAA is 2:2:
5.
4. The application according to claim 2 or 3, characterized in that, The hydrothermal reaction in step A is carried out at a temperature of 150-170°C for 10-14 hours; preferably, the hydrothermal reaction is carried out at a temperature of 160°C for 12 hours.
5. The application according to claim 2, characterized in that, In step B, the pH is adjusted to an alkaline value of 8.0-9.0; preferably, ammonia is used to adjust the pH to 8.
5.
6. The application according to claim 2 or 5, characterized in that, In step B, the mass ratio of the Zn2In2S5 nanomaterial to the dopamine or its salt is 1:0.1 to 1:0.
4.
7. The application according to claim 6, characterized in that, In step B, the mass ratio of the Zn2In2S5 nanomaterial to the dopamine or its salt is 1:0.
3.
8. The application according to claim 2, characterized in that, The in-situ polymerization reaction in step B is carried out at room temperature for 20-28 hours; preferably, the reaction time is 24 hours.
9. The application according to any one of claims 1-8, characterized in that, In the Zn2In2S5 / PDA composite material, polydopamine (PDA) is loaded onto the surface of Zn2In2S5 nanoflowers in a bulk island-like distribution, forming a pn-type heterojunction.
10. The application according to any one of claims 1-9, characterized in that, Under full-spectrum illumination, the surface temperature of the Zn2In2S5 / PDA composite material is more than 30°C higher than that of pure Zn2In2S5, and the light absorption range is extended from the ultraviolet region to the visible and near-infrared regions.