Novel modified porous nanosheet photocatalyst and preparation method thereof
By preparing modified In2O3 porous nanosheet photocatalysts, the difficulty of large-scale preparation of ZnO nanosphere catalysts was solved, efficient photocatalytic hydrogen production was achieved under mild conditions, and In2O3 nanosheets with excellent performance were formed.
Patent Information
- Application Number
- CN202511153094.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-18
- Publication Date
- 2025-10-17
AI Technical Summary
Existing technologies make it difficult to achieve large-scale preparation of highly uniform and high-yield ZnO nanosphere catalysts under mild conditions, and there is insufficient research on the impact of morphology control on photocatalytic performance.
Indium nitrate tetrahydrate was used as raw material, glucose and urea were used as polar solvents, and modified In2O3 porous nanosheet photocatalysts were prepared by stirring-ultrasound-assisted method. The complexation reaction between glucose and In metal ions formed a two-dimensional structure. Combined with hydrothermal reaction and calcination process, In2O3 nanosheets with excellent photocatalytic activity were prepared.
It exhibits excellent photocatalytic hydrogen production activity under visible light. The photocatalytic H2O2 production performance of In2O3 nanosheet photocatalyst exceeds 20mmol/L and has good stability.
Smart Images
Figure CN120790131A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the field of semiconductor photocatalysis, and particularly relates to a novel modified In2O3 porous nanosheet photocatalyst and a preparation method thereof. BACKGROUND
[0002] Hydrogen peroxide (H2O2) as an environmentally friendly oxidant plays an irreplaceable role in chemical synthesis, wastewater treatment and energy storage. However, the traditional industrial production method (such as anthraquinone method) has high energy consumption and serious pollution, and it is urgent to develop clean and sustainable alternative technologies. Therefore, the semiconductor photocatalytic technology for directly synthesizing H2O2 by using solar energy to drive water oxidation and oxygen reduction reaction (ORR) has been considered as a very promising green synthesis approach due to its mild reaction conditions and no secondary pollution.
[0003] Among semiconductor materials, ZnO has a band gap of 3.37 eV (~368 nm), and thus becomes an ideal material for detecting ultraviolet to near-ultraviolet light radiation. It is widely regarded as a core material in the field of optoelectronics, and is applied to piezoelectric devices, ultraviolet detectors, transparent conductive films and biosensors. In addition to the above applications, ZnO has formed a new research hotspot in the field of photocatalysis driven by ultraviolet light. The efficiency of photocatalytic reaction essentially depends on the surface catalytic process, and its activity is significantly affected by the morphology, size and microstructure of the catalyst. Therefore, researchers have successfully prepared ZnO nanostructure photocatalysts with different dimensions such as one-dimensional nanowires / rods, two-dimensional nanosheets and three-dimensional hierarchical microspheres through various strategies such as colloidal method, hydrothermal / solvothermal method, vapor deposition, electrochemical deposition and template-assisted synthesis. However, systematic research on the influence of morphology control on the performance of the same photocatalytic system is still insufficient, and in particular, the scale-up preparation of high-uniformity and high-yield ZnO nanosphere catalysts under mild conditions still faces challenges such as crystallinity regulation, agglomeration inhibition and surface active site optimization. SUMMARY
[0004] In order to solve the problems in the background art, the application provides a novel modified In2O3 porous nanosheet photocatalyst and a preparation method thereof.
[0005] The application specifically adopts the following technical solutions:
[0006] The preparation method of the novel modified In2O3 porous nanosheet photocatalyst is prepared by using indium nitrate tetrahydrate as a raw material, glucose and urea as polar solvents, and adopting a stirring-ultrasonic assisted method.
[0007] Further, the preparation method of the novel modified In2O3 porous nanosheet photocatalyst comprises the following steps:
[0008] (1) Dissolve indium nitrate tetrahydrate in deionized water and stir for a certain period of time.
[0009] (2) Then add a certain amount of glucose and urea to the above solution, stir for a certain period of time with a magnetic stirrer, and ultrasonic for a certain period of time to fully dissolve and mix.
[0010] (3) Then put the dissolved solution into an oven to have a hydrothermal reaction at a certain temperature for a period of time to obtain a precursor.
[0011] (4) Then put the obtained precursor into a muffle furnace and calcine at a certain temperature for a period of time to obtain an In2O3 porous nanosheet photocatalyst.
[0012] Further, the stirring for a certain period of time in step (1) is 30 min to 1 h.
[0013] Further, the certain amount of glucose and urea in step (2) is 4 to 6 g and 1 to 2 g, respectively.
[0014] Further, the stirring in step (2) is 30 min to 1 h and the ultrasonic is 15 to 30 min to fully dissolve.
[0015] Further, the certain temperature in step (3) is 130℃ to 150℃.
[0016] Further, the period of time in step (3) is 4 to 8 h.
[0017] Further, the certain temperature in step (4) is 500℃ to 600℃.
[0018] Further, the period of time in step (4) is 8 to 12 h.
[0019] The technical principle of the present invention is that glucose molecules contain multiple hydroxyl groups (-OH groups), which can coordinate with In metal ions through a lone pair of electrons on their oxygen atoms under acidic or alkaline conditions. This close interaction promotes the complexation reaction between glucose and In metal ions to form a stable In metal ion-glucose complex. In the classification of organic compounds, glucose is regarded as a small molecule, and its molecular structure is approximately planar and lacks a branched structure along the Z axis. This means that during the carbonization process, the In metal ion-glucose complex can undergo cross-linking, dehydration and carbonization in the horizontal direction, while the cross-linking in the vertical direction is hindered, and it is impossible to form a three-dimensional network structure like that produced after cellulose carbonization. As a result, the process tends to form a two-dimensional structure. The carbonized two-dimensional In metal ion-glucose complex is further heat-treated in air, and the In metal ions are oxidized to the corresponding In2O3. At the same time, the carbonized glucose is completely decomposed, and finally a two-dimensional structure In2O3 is formed.
[0020] The present invention has the following beneficial effects:
[0021] (1) In the present invention, indium nitrate tetrahydrate is used as the raw material, and glucose and urea are used as polar solvents, and the preparation is carried out by a stirring-ultrasound-assisted method. Among them, the polar solvent mixture of glucose and urea can adjust the polarity of the solvent during the reaction process. The vacuum condition is to prevent the In2O3 nanosheets from being oxidized during the preparation process, and at the same time, to extract the dissolved oxygen in the solvent, reduce the interfacial partial pressure, and reduce the surface tension of the solvent molecules. The stirring process is to fully mix the reaction materials and ensure that the reaction materials are evenly distributed in the reaction system. On the other hand, it prevents product precipitation and maintains the temperature uniformity of the reaction system.
[0022] (2) The present invention adopts a conventional solvent thermal method to prepare In2O3 material. The In2O3 nanosheet photocatalyst prepared by this method exhibits excellent photocatalytic hydrogen production activity under visible light. BRIEF DESCRIPTION OF THE DRAWINGS
[0023] Figure 1 This is a scanning electron microscope image of the In2O3 porous nanosheet photocatalyst prepared in Example 1 of the present invention.
[0024] Figure 2 This is the XRD pattern of the In2O3 porous nanosheet photocatalyst prepared in Example 1 of the present invention.
[0025] Figure 3 This is a performance diagram of the In2O3 porous nanosheet photocatalyst prepared in Example 1 of the present invention, showing an ultraviolet fluorescence spectrum.
[0026] Figure 4Figure 1 shows the photocatalytic activity of the In2O3 porous nanosheet photocatalyst prepared in Example 1 of the present application in evaluating the photocatalytic activity of H2O2 conversion under light irradiation. DETAILED DESCRIPTION
[0027] In order for those skilled in the art to better understand the technical solutions of the present application, the present application will be described in further detail below with reference to the accompanying drawings.
[0028] Example 1
[0029] A preparation method of a novel modified In2O3 porous nanosheet photocatalyst, comprising the following steps:
[0030] (1) Dissolve indium nitrate tetrahydrate in deionized water and stir for 30 min.
[0031] (2) Then add 5 g of glucose and 1 g of urea to the above solution, stir with a magnetic stirrer for 30 min, and ultrasonically dissolve and mix for 15 min.
[0032] (3) Then place the dissolved solution in an oven and perform a hydrothermal reaction at 140℃, and obtain a precursor after 6 h.
[0033] (4) Then place the obtained precursor in a muffle furnace and calcine at 550℃ for 10 h to obtain an In2O3 porous nanosheet photocatalyst.
[0034] The In2O3 porous nanosheet photocatalyst prepared in Example 1 of the present application was characterized, and the results are shown in Figures 1-4
[0035] As can be seen from Figure 1 , Figure 1 (a) is a small-magnification SEM image, Figure 1 (b) and Figure 1 (c) are large-magnification SEM images, all of which show that the In2O3 presents a sheet structure.
[0036] As can be seen from Figure 2 , the synthesized In2O3 has good crystallinity.
[0037] As can be seen from Figure 3 , the synthesized In2O3 has an absorption edge of 373 nm and a band gap of 3.58 eV
[0038] As can be seen from Figure 4 , the synthesized In2O3 has a H2O2 photocatalytic production performance of more than 20 mmol / L and good stability.
[0039] Example 2
[0040] A preparation method of a novel modified In2O3 porous nanosheet photocatalyst, comprising the following steps:
[0041] (1) Dissolve indium nitrate tetrahydrate in deionized water and stir for 30 min.
[0042] (2) Then add 5 g of glucose and 1 g of urea to the above solution, stir with a magnetic stirrer for 30 min, and ultrasonic for 15 min to fully dissolve and mix.
[0043] (3) Then put the dissolved solution into an oven to undergo hydrothermal reaction at 150°C, and obtain the precursor after 6h.
[0044] (4) Then put the obtained precursor into a muffle furnace and calcine at 550°C for 10h to obtain the In2O3 porous nanosheet photocatalyst.
[0045] Example 3
[0046] A preparation method of a new modified In2O3 porous nanosheet photocatalyst, comprising the following steps:
[0047] (1) Dissolve indium nitrate tetrahydrate in deionized water and stir for 30 min.
[0048] (2) Then add 5 g of glucose and 1 g of urea to the above solution, stir with a magnetic stirrer for 30 min, and ultrasonic for 15 min to fully dissolve and mix.
[0049] (3) Then put the dissolved solution into an oven to undergo hydrothermal reaction at 140°C, and obtain the precursor after 6h.
[0050] (4) Then put the obtained precursor into a muffle furnace and calcine at 500°C for 10h to obtain the In2O3 porous nanosheet photocatalyst.
[0051] Comparative Example 1
[0052] A preparation method of a nanosheet photocatalyst, comprising the following steps:
[0053] (1) Dissolve indium nitrate tetrahydrate in deionized water and stir for 30 min.
[0054] (2) Then add 4 g of glucose and 1 g of urea to the above solution, stir with a magnetic stirrer for 30 min, and ultrasonic for 15 min to fully dissolve and mix.
[0055] (3) Then put the dissolved solution into an oven to undergo hydrothermal reaction at 150°C, and obtain the precursor after 6h.
[0056] (4) Then put the obtained precursor into a muffle furnace and calcine at 550°C for 10h to obtain the In2O3 porous nanosheet photocatalyst.
[0057] Comparative Example 2
[0058] A method for preparing a nanosheet photocatalyst comprises the following steps:
[0059] (1) Dissolve indium nitrate tetrahydrate in deionized water and stir for 30 minutes.
[0060] (2) Then, 5 g of glucose and 2 g of urea were added to the above solution, stirred with a magnetic stirrer for 30 min, and ultrasonicated for 15 min to fully dissolve and mix.
[0061] (3) The dissolved solution was then placed in an oven for hydrothermal reaction at 140 °C, and the precursor was obtained after 6 h.
[0062] (4) The obtained precursor was then placed in a muffle furnace and calcined at 600 °C for 10 h to obtain In2O3 porous nanosheet photocatalyst.
[0063] Comparative Example 3
[0064] A method for preparing a nanosheet photocatalyst comprises the following steps:
[0065] (1) Dissolve indium nitrate tetrahydrate in deionized water and stir for 30 minutes.
[0066] (2) Then, 4 g of glucose and 2 g of urea were added to the above solution, stirred with a magnetic stirrer for 30 min, and ultrasonicated for 15 min to fully dissolve and mix.
[0067] (3) The dissolved solution was then placed in an oven for hydrothermal reaction at 150 °C, and the precursor was obtained after 6 h.
[0068] (4) The obtained precursor was then placed in a muffle furnace and calcined at 600 °C for 10 h to obtain In2O3 porous nanosheet photocatalyst.
[0069] The above description is only used to understand the method and core idea of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made to the present invention without departing from the principles of the present invention. These improvements and modifications also fall within the scope of protection of the rights of the present invention.
Claims
1. A method for preparing a novel modified porous nanosheet photocatalyst, characterized by: The preparation method is prepared by using indium nitrate tetrahydrate as raw material, glucose and urea as polar solvents and adopting a stirring-assisted method.
2. The method for preparing the novel modified porous nanosheet photocatalyst according to claim 1, characterized in that: The following steps are involved: (1) Dissolve indium nitrate tetrahydrate in deionized water and stir for a certain period of time; (2) Then, a certain amount of glucose and urea were added to the above solution, stirred with a magnetic stirrer for a certain period of time, and ultrasonicated for a certain period of time to fully dissolve and mix; (3) The dissolved solution is then placed in an oven to undergo a hydrothermal reaction at a certain temperature, and a precursor is obtained after a period of time; (4) The obtained precursor is then placed in a muffle furnace and calcined at a certain temperature for a period of time to obtain In2O3 porous nanosheet photocatalyst.
3. The method for preparing the novel modified porous nanosheet photocatalyst according to claim 2, characterized in that: The stirring time in step (1) is 30 minutes to 1 hour.
4. The method for preparing the novel modified porous nanosheet photocatalyst according to claim 2, characterized in that: The certain amount of glucose and urea described in step (2) are 4-6 g and 1-2 g respectively.
5. The method for preparing the novel modified porous nanosheet photocatalyst according to claim 2, characterized in that: In step (2), the mixture is stirred for 30 min to 1 h and ultrasonicated for 15 to 30 min to fully dissolve the mixture.
6. The method for preparing the novel modified porous nanosheet photocatalyst according to claim 2, characterized in that: The certain temperature in step (3) is 130°C to 150°C.
7. The method for preparing the novel modified porous nanosheet photocatalyst according to claim 2, characterized in that: The period of time in step (3) is 4 to 8 hours.
8. The method for preparing the novel modified porous nanosheet photocatalyst according to claim 2, characterized in that: The certain temperature in step (4) is 500°C to 600°C.
9. The method for preparing the novel modified porous nanosheet photocatalyst according to claim 2, characterized in that: The period of time in step (4) is 8 to 12 hours.
10. A novel modified porous nanosheet photocatalyst prepared according to the method according to any one of claims 1 to 9.