A method for constructing a Cu-TiO2 / RP heterostructure and application thereof
By constructing a Cu-TiO2/RP heterostructure, the problem of TiO2 catalyst response to ultraviolet light was solved, enabling the utilization of visible light and carrier separation, thereby improving photocatalytic efficiency and reducing costs.
Patent Information
- Application Number
- CN202410404971.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-04-07
- Publication Date
- 2025-12-16
- Estimated Expiration
- 2044-04-07
AI Technical Summary
Traditional TiO2 semiconductor catalysts have a large band gap, so they can only respond to ultraviolet light and cannot effectively utilize visible light, making them difficult to apply in real life.
A Cu-TiO2/RP heterostructure was constructed by pretreatment of red phosphorus RP, thermal treatment of the mixture, and microwave hydrothermal synthesis to form a Cu-TiO2/RP heterojunction, thereby improving photocatalytic efficiency and expanding the photoreaction range.
It achieves full utilization of the solar spectrum, improves photocatalytic performance, effectively separates charge carriers, reduces costs, and does not rely on precious metal co-catalysts.
Smart Images
Figure CN118287116B_ABST
Abstract
Description
Technical Field
[0001] This application relates to the field of photocatalytic materials, and more specifically, to a method for constructing and applying a Cu-TiO2 / RP heterostructure. Background Technology
[0002] With increasing public concern about energy demand and environmental issues, developing sustainable and clean energy sources to replace fossil fuels has become a primary concern. Hydrogen, due to its high energy content, environmental friendliness, and recyclability, is considered the most viable alternative to fossil fuels. Photocatalysis, which converts solar energy into H2, is considered one of the most economical and environmentally friendly solutions. Since Fujishima and Honda discovered in 1972 that TiO2 could decompose water into O2 and H2 under light conditions, TiO2 has rapidly gained popularity due to its low cost, non-toxicity, and good stability. Meanwhile, many inorganic semiconductors, such as metal oxides and sulfides, have also attracted widespread attention in the field of photocatalytic hydrogen evolution. Their simple synthesis methods, controllable morphologies, and suitable conduction band positions have made them increasingly attractive to researchers in recent years.
[0003] However, traditional semiconductor catalysts such as TiO2 have a large band gap, which means they can only respond to ultraviolet light and cannot absorb visible light, making them difficult to apply in real life. Summary of the Invention
[0004] This application aims to address at least one of the technical problems existing in the prior art. To this end, this application proposes a method for constructing Cu-TiO2 / RP heterostructures and their applications.
[0005] In a first aspect, this application provides a method for constructing a Cu-TiO2 / RP heterostructure, comprising the following steps:
[0006] Step A: Pretreatment of red phosphorus RP: Disperse 2g of commercial red phosphorus RP in 80ml of water and react at 190℃ for 12 hours to remove the oxide layer and reduce the particle size;
[0007] Step B: Measure the amount of DMF in the formula and stir it in a flask. Add the amount of terephthalic acid, methanol and tetrabutyl titanate in the formula and heat treat. Then centrifuge, wash and dry to obtain Mil-125.
[0008] Step C: Measure the mixture of Mil-125, CuCl2, water and 0.4g of PVP according to the formula, stir, centrifuge, wash with water, dry, heat treat and cool to obtain Cu-TiO2;
[0009] Step D: Mix Cu-TiO2 and red phosphorus RP according to the formula and sonicate, then synthesize by microwave hydrothermal method.
[0010] The method for constructing a Cu-TiO2 / RP heterostructure according to an embodiment of this application has the following advantages: low cost; compared with other titanium dioxide photocatalysts that use noble metals as co-catalysts, the Cu-TiO2 / RP catalyst of this application does not require noble metals as co-catalysts and can still achieve the same effect as titanium dioxide photocatalysts that use noble metals as co-catalysts; high photocatalytic efficiency; due to the doping of Cu and the construction of the heterostructure, the photocatalytic efficiency is improved, and the photoreaction range is expanded; by designing the Cu-TiO2 covalent organic framework structure and the heterostructure of red phosphorus, the photocatalyst can make fuller use of the solar spectrum and effectively separate charge carriers, thereby improving the photocatalytic performance.
[0011] Preferably, the Cu-TiO2 / RP heterostructure comprises the raw materials for synthesizing Mil-125, copper chloride, red phosphorus, methanol, and water.
[0012] Preferably, in the synthesis of Cu-TiO2 / RP, the mass ratio of Cu-TiO2 to red phosphorus RP is 200:10~40.
[0013] Preferably, the raw materials for synthesizing Mil-125 are 270 ml DMF, 15 g terephthalic acid, 30 ml methanol and 7.8 ml tetrabutyl titanate.
[0014] Preferably, the heat treatment temperature of the mixture of 270ml DMF, 15g terephthalic acid, 30ml methanol and 7.8ml tetrabutyl titanate is 130℃, and the reaction time is 20 hours.
[0015] Preferably, 0.5 g of Mil-125 and 6.8 mg of CuCl2 are dissolved in 80 ml of water and stirred for 8 hours. After centrifugation, washing, and drying, Cu-Mil-125 is obtained.
[0016] Preferably, Cu-TiO2 is obtained by heating Cu-Mil-125 in a muffle furnace at a rate of 10 °C / min and holding it at 450 °C for 4 hours, followed by cooling after heat treatment.
[0017] Preferably, Cu-TiO2 and red phosphorus RP are mixed at mass ratios of 200:10, 200:20, 200:30 and 200:40, respectively, and 50 ml of pure water is added to each mixture. The mixture is then sonicated for 20 minutes, and then microwave hydrothermal synthesis of Cu-TiO2 / RP heterostructure is performed on the mixture.
[0018] Preferably, the heating rate for microwave hydrothermal synthesis of Cu-TiO2 / RP heterostructures is 2°C / min until a temperature of 120°C is reached. After an incubation period of 2 hours, the mixture is cooled to room temperature, and the resulting samples are washed to obtain 5%RP / TiO2, 10%RP / TiO2, 15%RP / TiO2, and 20%RP / TiO2, respectively.
[0019] On the other hand, this application provides a Cu-TiO2 / RP heterostructure prepared by a component method for photocatalytic reaction of titanium dioxide. Attached Figure Description
[0020] To more clearly illustrate the technical solutions of the embodiments of this application, the drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of this application and should not be regarded as a limitation of the scope. For those skilled in the art, other related drawings can be obtained from these drawings without creative effort.
[0021] Figure 1 This is a flowchart illustrating the preparation of a Cu-TiO2 / RP heterostructure photocatalytic material according to an embodiment of this application.
[0022] Figure 2 (a) shows the photocatalytic H2 evolution capability of Cu-TiO2 composite materials with different red phosphorus RP contents prepared according to the embodiments of this application; (b) is a cyclic test of continuous photocatalytic H2 evolution of 10% RP / TiO2; (c) is the EIS Nyquist plot of TiO2, 5% RP / TiO2, 10% RP / TiO2, 15% RP / TiO2 and 20% RP / TiO2; and (d) is the transient photocurrent response measurement.
[0023] Figure 3 The Cu-TiO2 / RP heterostructure photocatalytic material prepared according to the embodiments of this application was subjected to XRD testing, TEM testing and nitrogen adsorption evaluation.
[0024] Figure 4 Fluorescence spectral analysis of the Cu-TiO2 / RP heterostructure photocatalytic material prepared according to the embodiments of this application;
[0025] Figure 5 XPS analysis of the Cu-TiO2 / RP heterostructure photocatalytic material prepared according to the embodiments of this application. Detailed Implementation
[0026] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of this application, not all of them. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.
[0027] like Figures 1-5 As shown, a method for constructing a Cu-TiO2 / RP heterostructure according to an embodiment of this application is as follows:
[0028] 2g of commercial red phosphorus RP was dispersed in 80ml of water and reacted at 190℃ for 12 hours to remove the oxide layer and reduce particle size. In a 500ml round-bottom flask, 270ml of DMF, 15g of terephthalic acid, 30ml of methanol, and 7.8ml of tetrabutyl titanate were dissolved. After complete dispersion, the mixture was heated to 130℃ and reacted for 20 hours. After centrifugation, washing, and drying, Mil-125 was obtained. 0.5g of Mil-125 and 6.8mg of CuCl2 were mixed in 80ml of water and stirred for 8 hours. After centrifugation, washing, and drying, Cu-Mil-125 was obtained. The sample was heated in a muffle furnace at a rate of 10℃ / min, then raised to 450℃ and held at that temperature for 4 hours. After heat treatment, the sample was allowed to cool, forming Cu-TiO2. Cu-TiO2 and red phosphorus RP were mixed at mass ratios of 200:10, 200:20, 200:30, and 200:40. 50 ml of pure water was added to the mixture, and the mixture was sonicated for 20 minutes. The mixture was then subjected to microwave hydrothermal synthesis. The heating rate used in this study was set to 2 °C / min until a temperature of 120 °C was reached, followed by an incubation period of 2 hours. After cooling to room temperature, the samples were washed and dried, and named 5% RP / TiO2, 10% RP / TiO2, 15% RP / TiO2, and 20% RP / TiO2, respectively.
[0029] The following specific implementation examples further illustrate this application:
[0030] Example 1
[0031] A. 2g of commercial red phosphorus RP was dispersed in 80ml of water and reacted at 190°C for 12 hours to remove the oxide layer and reduce particle size. In a 500ml round-bottom flask, 270ml of DMF, 15g of terephthalic acid, 30ml of methanol, and 7.8ml of tetrabutyl titanate were taken. After complete dispersion, the mixture was heated to 130°C and reacted for 20 hours. After centrifugation, washing, and drying, Mil-125 was obtained. 0.5g of Mil-125 and 6.8mg of CuCl2 were mixed in 80ml of water and stirred for 8 hours. After centrifugation, washing, and drying, Cu-Mil-125 was obtained. After heating in a muffle furnace at a rate of 10°C / min, the sample was raised to 450°C and held at this temperature for 4 hours. After heat treatment, the sample was allowed to cool, forming Cu-TiO2.
[0032] B. Cu-TiO2 and red phosphorus RP were mixed at a mass ratio of 200:10. 50 ml of pure water was added to the mixture, and the mixture was sonicated for 20 minutes. The mixture was then subjected to microwave hydrothermal synthesis. The heating rate used in this study was set to 2 °C / min until a temperature of 120 °C was reached, followed by a 2-hour incubation period. After cooling to room temperature, the sample was washed, dried, and named 5% RP / TiO2.
[0033] Example 2
[0034] A. 2g of commercial red phosphorus RP was dispersed in 80ml of water and reacted at 190℃ for 12 hours to remove the oxide layer and reduce the particle size. In a 500ml round-bottom flask, 270ml of DMF, 15g of terephthalic acid, 30ml of methanol, and 7.8ml of tetrabutyl titanate were taken. After complete dispersion, the mixture was heated to 130℃ and reacted for 20 hours. After centrifugation, washing, and drying, Mil-125 was obtained. 0.5g of Mil-125 and 6.8mg of CuCl2 were mixed in 80ml of water and stirred for 8 hours. After centrifugation, washing, and drying, Cu-Mil-125 was obtained. After heating in a muffle furnace at a rate of 10℃ / min, the sample was raised to 450℃ and held at that temperature for 4 hours. After heat treatment, the sample was allowed to cool, forming Cu-TiO2.
[0035] B.Cu-TiO2 and red phosphorus RP were mixed at a mass ratio of 200:10. 50 ml of pure water was added to the mixture, and the mixture was sonicated for 20 minutes. The mixture was then subjected to microwave hydrothermal synthesis. The heating rate used in this study was set to 2 °C / min until a temperature of 120 °C was reached, followed by a 2-hour incubation period. After cooling to room temperature, the samples were washed, dried, and named 10%RP / TiO2.
[0036] Example 3
[0037] A. 2g of commercial red phosphorus RP was dispersed in 80ml of water and reacted at 190℃ for 12 hours to remove the oxide layer and reduce the particle size. In a 500ml round-bottom flask, 270ml of DMF, 15g of terephthalic acid, 30ml of methanol, and 7.8ml of tetrabutyl titanate were taken. After complete dispersion, the mixture was heated to 130℃ and reacted for 20 hours. After centrifugation, washing, and drying, Mil-125 was obtained. 0.5g of Mil-125 and 6.8mg of CuCl2 were mixed in 8ml of water and stirred for 8 hours. After centrifugation, washing, and drying, Cu-Mil-125 was obtained. After heating in a muffle furnace at a rate of 10℃ / min, the sample was raised to 450℃ and held at that temperature for 4 hours. After heat treatment, the sample was allowed to cool, forming Cu-TiO2.
[0038] B. Cu-TiO2 and red phosphorus RP were mixed at a mass ratio of 200:20. 50 ml of pure water was added to the mixture, and the mixture was sonicated for 20 minutes. The mixture was then subjected to microwave hydrothermal synthesis. The heating rate used in this study was set to 2 °C / min until a temperature of 120 °C was reached, followed by a 2-hour incubation period. After cooling to room temperature, the samples were washed, dried, and named 15% RP / TiO2.
[0039] Example 4
[0040] A. 2g of commercial red phosphorus RP was dispersed in 80ml of water and reacted at 190℃ for 12 hours to remove the oxide layer and reduce the particle size. In a 500ml round-bottom flask, 270ml of DMF, 15g of terephthalic acid, 30ml of methanol, and 7.8ml of tetrabutyl titanate were taken. After complete dispersion, the mixture was heated to 130℃ and reacted for 20 hours. After centrifugation, washing, and drying, Mil-125 was obtained. 0.5g of Mil-125 and 6.8mg of CuCl2 were mixed in 80ml of water and stirred for 8 hours. After centrifugation, washing, and drying, Cu-Mil-125 was obtained. After heating in a muffle furnace at a rate of 10℃ / min, the sample was raised to 450℃ and held at that temperature for 4 hours. After heat treatment, the sample was allowed to cool, forming Cu-TiO2.
[0041] B. Cu-TiO2 and red phosphorus RP were mixed at a mass ratio of 200:20. 50 ml of pure water was added to the mixture, and the mixture was sonicated for 20 minutes. The mixture was then subjected to microwave hydrothermal synthesis. The heating rate used in this study was set to 2 °C / min until a temperature of 120 °C was reached, followed by an incubation period of 2 hours. After cooling to room temperature, the samples were washed, dried, and named 20% RP / TiO2.
[0042] Example 5
[0043] The Cu-TiO2 / RP heterostructure photocatalytic material prepared in Example 2 was subjected to fluorescence spectroscopy analysis, electron microscopy analysis, and photocatalytic water splitting performance testing, as detailed below:
[0044] A. Analysis of the hydrogen production performance of the Cu-TiO2 / RP heterostructure photocatalytic material prepared in this invention, as follows: Figure 2 As shown, the hydrogen production performance of pure TiO2 and TiO2 doped with red phosphorus RP at different molar ratios was tested. A 300W xenon lamp was used as the light source, methanol was used as the hole sacrificial agent, and the reactor was connected to cooling circulating water to maintain 20℃. The products were characterized by gas chromatography.
[0045] The photocatalytic H2 evolution capabilities of a series of Cu-TiO2 composites with different red phosphorus (RP) contents were investigated. (b) Cyclic experiments of continuous photocatalytic H2 evolution with 10% RP / TiO2; (c) EIS Nyquist plots of TiO2, 5% RP / TiO2, 10% RP / TiO2, 15% RP / TiO2, and 20% RP / TiO2; and (d) transient photocurrent response measurements were also performed. A 300W xenon lamp was used as the light source, methanol as the hole sacrificial agent, and the reactor was connected to a cooling circulating water system maintained at 20°C. The products were characterized by gas chromatography.
[0046] B. The Cu-TiO2 / RP heterostructure photocatalytic material prepared in this invention was subjected to XRD, TEM, and nitrogen adsorption tests as follows: Figure 3 As shown. The crystal structure and morphology were characterized by powder X-ray diffraction (XRD, Smartlab SE, Japan) and transmission electron microscopy (TEM, FEITalos F200X). The powder area was evaluated based on the nitrogen adsorption isotherm at 77 K. XRD patterns of TiO2, 5%RP / TiO2, 10%RP / TiO2, 15%RP / TiO2 and 20%RP / TiO2 (b) TEM image of RP / TiO2 (ch) N2 adsorption and desorption isotherms of TiO2, 5%RP / TiO2, 10%RP / TiO2, 15%RP / TiO2 and 20%RP / TiO2.
[0047] C. Fluorescence spectral analysis of the Cu-TiO2 / RP heterostructure photocatalytic material prepared in this invention is as follows: Figure 4 As shown, the photogenerated electron-hole recombination rate and lifetime of RP / TiO2 were studied using photoluminescence (PL, FLS1000) and TRPL.
[0048] D. XPS analysis was performed on the Cu-TiO2 / RP heterostructure photocatalytic material prepared in this invention, such as... Figure 5As shown, X-ray photoelectron spectroscopy (XPS, K-Alpha+) was used to verify the material synthesis. XPS tests were performed on the samples, and the results are as follows. Figure 5 As shown in (a and b).
[0049] Before the improvement, the hydrogen evolution performance of pure TiO2 was only 7.26 mmol g⁻¹ h⁻¹. After loading different mass ratios of RP (5% RP / TiO2, 10% RP / TiO2, 15% RP / TiO2, and 20% RP / TiO2), its hydrogen evolution performance was improved to 18.75 mmol g⁻¹ h⁻¹. -1 h -1 18.748 mmol / g -1 h -1 20.328 mmol / g -1 h -1 18.928 mmol / g -1 h -1 and 17.108 mmolg - 1 h -1 Through screening processes with different RP ratios, it was determined that 10% RP / TiO2 exhibited the highest hydrogen production performance, 2.8 times higher than TiO2. In the embodiments of this application, Cu was doped during the modification of titanium dioxide, forming a heterostructure with red phosphorus, which effectively promoted the separation of photogenerated carriers in the heterojunction, expanded the photoreaction range, and greatly improved the photocatalytic hydrogen production efficiency of titanium dioxide. The above are merely preferred embodiments of this application and are not intended to limit this application. For those skilled in the art, this application can have various modifications and variations. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.
Claims
1. A method for constructing a Cu-TiO2 / RP heterostructure, characterized in that, Includes the following steps: Step A: Pretreatment of red phosphorus RP: Disperse 2g of commercial red phosphorus RP in 80ml of water and react at 190℃ for 12 hours to remove the oxide layer and reduce the particle size; Step B: Measure the amount of DMF in the formula and stir it in a flask. Add the amount of terephthalic acid, methanol and tetrabutyl titanate in the formula and heat treat. Then centrifuge, wash and dry to obtain Mil-125. Step C: Measure the mixture of Mil-125, CuCl2, water and 0.4g of PVP according to the formula, stir, centrifuge, wash with water, dry, heat treat and cool to obtain Cu-TiO2; Step D: Mix Cu-TiO2 and red phosphorus RP according to the formula and sonicate, then synthesize by microwave hydrothermal method.
2. The method for constructing a Cu-TiO2 / RP heterostructure as described in claim 1, characterized in that: The Cu-TiO2 / RP heterostructure includes the raw materials for synthesizing Mil-125, copper chloride, red phosphorus, methanol, and water.
3. The method for constructing a Cu-TiO2 / RP heterostructure as described in claim 1, characterized in that: In the synthesis of Cu-TiO2 / RP, the mass ratio of Cu-TiO2 to red phosphorus RP is 200:10~40.
4. The method for constructing a Cu-TiO2 / RP heterostructure as described in claim 1, characterized in that: The raw materials for the synthesis of Mil-125 are 270ml DMF, 15g terephthalic acid, 30ml methanol and 7.8ml tetrabutyl titanate.
5. The method for constructing a Cu-TiO2 / RP heterostructure as described in claim 4, characterized in that: The heat treatment of a mixture of 270 ml DMF, 15 g terephthalic acid, 30 ml methanol and 7.8 ml tetrabutyl titanate was carried out at 130 °C for 20 hours.
6. The method for constructing a Cu-TiO2 / RP heterostructure as described in claim 1, characterized in that: Take 0.5g of Mil-125 and 6.8mg of CuCl2, add them to 80ml of water and stir for 8 hours. After centrifugation, washing and drying, Cu-Mil-125 is obtained.
7. The method for constructing a Cu-TiO2 / RP heterostructure as described in claim 6, characterized in that: Cu-TiO2 was obtained by heating Cu-Mil-125 in a muffle furnace at a rate of 10 °C / min and holding it at 450 °C for 4 hours, followed by cooling after heat treatment.
8. The method for constructing a Cu-TiO2 / RP heterostructure as described in claim 1, characterized in that: Cu-TiO2 and red phosphorus RP were mixed at mass ratios of 200:10, 200:20, 200:30 and 200:40, respectively. 50 ml of pure water was added to each mixture, and the mixture was sonicated for 20 minutes. Then, the mixture was subjected to microwave hydrothermal synthesis to synthesize Cu-TiO2 / RP heterostructures.
9. The method for constructing a Cu-TiO2 / RP heterostructure as described in claim 8, characterized in that: The heating rate for microwave hydrothermal synthesis of Cu-TiO2 / RP heterostructures was 2℃ / min until a temperature of 120℃ was reached. After an incubation period of 2 hours, the mixture was cooled to room temperature, and the resulting samples were washed to obtain 5%RP / TiO2, 10%RP / TiO2, 15%RP / TiO2, and 20%RP / TiO2, respectively.
10. A Cu-TiO2 / RP heterostructure prepared by the method of any one of claims 1-9 is applied to the photocatalytic reaction of titanium dioxide.