Preparation method of Ba0. 8Ce0. 2TiO3 thin film material for thermal-photoelectric catalysis
By doping BaTiO3 with Ce ions to prepare Ba0.8Ce0.2TiO3 thin films, the problems of wide band gap, poor light absorption and fast carrier recombination in thermo-photoelectrocatalysis of BaTiO3 were solved, and the performance of thermo-photoelectrocatalysis was improved by achieving high efficiency.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- TIANJIN CHENGJIAN UNIV
- Filing Date
- 2024-10-14
- Publication Date
- 2026-04-17
AI Technical Summary
BaTiO3 suffers from problems in thermo-photoelectrocatalysis, such as a wide band gap leading to poor visible light absorption, rapid recombination of photogenerated carriers, low photoelectrocatalytic degradation performance, and low pyroelectrocatalytic efficiency of nanostructures.
Ba0.8Ce0.2TiO3 thin films were prepared by doping BaTiO3 with Ce ions, and the band structure and Curie temperature were adjusted to improve the light absorption performance and carrier separation efficiency.
It broadens the light absorption range, reduces the recombination of photogenerated electron-hole pairs, improves the thermal-photoelectrocatalytic performance, and is low in cost and simple to operate.
Smart Images
Figure CN121869337A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of thermal-photoelectrocatalytic materials, specifically relating to a Ba 0.8 Ce 0.2 A method for preparing TiO3 semiconductor thermal-photoelectrocatalytic thin films. Background Technology
[0002] With the development of the textile industry, a large amount of various dye wastewater is generated every year. Global annual dye consumption reaches 1×10⁻⁶. 6 Tons, global organic dye production exceeds 1×10 6 The typical characteristics of dye wastewater are high chemical oxygen demand (COD) and color, containing salts and chlorides, making it difficult to degrade. The discharge of dye wastewater into water bodies has seriously threatened aquatic environmental safety. Therefore, the degradation and treatment of organic dye pollutants in the aquatic environment has received considerable attention. Utilizing the thermo-photoelectrocatalytic properties of semiconductors for pollutant degradation is considered the most efficient method due to its unique advantages. BaTiO3, as an n-type semiconductor, exhibits good chemical stability and suitable band positions for pollutant degradation. However, the relatively wide band gap of BaTiO3 (~3.1 eV) results in poor visible light absorption, and rapid carrier recombination limits catalytic performance. Furthermore, the separation efficiency of photogenerated carriers in BaTiO3 is not ideal, reducing photoelectrocatalytic degradation performance. The pyroelectric catalytic degradation efficiency of nanostructured BaTiO3 materials remains low, and its Curie temperature (Tc) deviates significantly from the ambient temperature required for effective catalysis. Doping BaTiO3 with heterovalent ions can improve catalytic efficiency. By adjusting the band structure and Tc to match the actual operating temperature, the light absorption performance can be improved, ultimately enhancing the catalytic efficiency. Summary of the Invention
[0003] To address the aforementioned problems with BaTiO3 in thermo-photocatalysis and further improve the thermo-photocatalytic performance of BaTiO3 films, a BaTiO3-based thermo-photocatalytic method was invented. 0.8 Ce 0.2 Method for preparing TiO3 membrane.
[0004] To achieve the above objectives, the present invention provides a Ba for thermo-photocatalysis. 0.8 Ce 0.2 The preparation method of TiO3 composite thin film material includes the following steps:
[0005] (1) Prepare a hydrochloric acid solution of a certain concentration. Add a certain amount of tetrabutyl titanate to the dilute hydrochloric acid solution and stir for a period of time. After the white suspension disappears, the precursor solution is obtained. Place the cleaned FTO at a 45° angle into a 25ml container.
[0006] The conductive surface of the reactor liner faces downwards. The prepared solution is then poured into the reactor liner and sealed. The reactor is then subjected to hydrothermal reaction in an electrically heated drying oven at a specific temperature for a certain time. Afterwards, the reacted sample is washed, filtered, and dried to obtain a TiO2 precursor film.
[0007] (2) A certain amount of diethylene glycol, isopropanol, and distilled water were added to a beaker and stirred for a certain period of time. After thorough mixing, a certain amount of Ba(OH)₂·8H₂O and Ce(NO)₃·6H₂O were added to the solution and stirred for a certain period of time. The prepared FTO containing TiO₂ precursor was then placed tilted in the lining of the reactor with the conductive surface facing down. After reacting at a certain temperature for a certain period of time, the prepared sample was washed and dried. The dried sample was then calcined in a muffle furnace for a certain period of time to obtain highly crystalline Ba. 0.8 Ce 0.2 TiO3 thin film.
[0008] In step (1) above, the volume of the tetrabutyl titanate is 0.500 to 1.000 ml, the hydrothermal reaction temperature and time are 160℃ to 180℃ and 18 to 24 h respectively, and the product is dried in a drying oven for 1 h.
[0009] In step (2) above, the concentration of barium hydroxide octahydrate is 0.500-1.000 mM, the temperature and time of the hydrothermal reaction are 180-200℃ and 6-10h respectively, the drying temperature in the drying oven is 60℃, and then FTO is placed in a crucible for heat treatment for 2h at a temperature of 450-550℃.
[0010] The invention provides a Ba for thermo-photocatalysis 0.8 Ce 0.2 The preparation method of TiO3 thin film material has the following beneficial effects:
[0011] (1) The present invention can effectively broaden the light absorption range and reduce the recombination of photogenerated electron-hole pairs.
[0012] (2) The preparation method of the present invention is simple and easy to operate, and the overall cost is low.
[0013] (3) Ba obtained by the present invention 0.8 Ce 0.2 TiO3 thin film materials have low Curie temperature and small particle radius, resulting in excellent thermo-photocatalytic catalytic performance. Attached Figure Description
[0014] Figure 1 Ba is the present invention 0.8 Ce 0.2 Scanning electron microscope image of TiO3 thin film. Detailed Implementation
[0015] The following embodiments are intended to enable those skilled in the art to gain a more comprehensive understanding of the present invention, but do not limit the invention in any way.
[0016] Example 1
[0017] (1) Add 10 ml of distilled water and 5 ml of hydrochloric acid (36-38%) to a beaker and stir slowly for 10 min at a constant temperature of 25°C using a magnetic stirrer. Then, slowly add 0.15 ml of tetrabutyl titanate solution dropwise to the stirred mixture and stir slowly for another 10 min. Next, place the cleaned FTO at a 45° angle in the liner of a 25 ml reactor, with the conductive surface facing down. Then pour the prepared solution into the liner of the reactor and seal it. Perform a hydrothermal reaction in an electric heating drying oven at 160°C for 24 h, then cool and remove it, and dry it in a drying oven at 60°C to obtain a TiO2 film.
[0018] (2) Add 5 ml of anhydrous ethanol, 5 ml of diethylene glycol, 1.5 ml of isopropanol, and 7 ml of distilled water to a beaker in sequence, and stir slowly for 10 min at a constant temperature of 25°C using a magnetic stirrer. Then, add 0.1893 g of Ba(OH)₂·8H₂O solid particles and 0.0652 g of Ce(NO₃)₃·6H₂O to the stirred solution, and stir slowly again until all the solid particles are dissolved. Then, place the FTO containing the prepared TiO₂ at a 45° angle in the liner of a 25 ml reactor, with the conductive surface facing down. Then pour the prepared solution into the liner of the reactor and seal it. Perform a hydrothermal reaction in an electric heating drying oven at 200°C for 6 h, then cool and remove it, dry it in a drying oven at 60°C, and then calcine it in a muffle furnace at 500°C for 1 h to obtain highly crystalline Ba. 0.8 Ce 0.2 TiO3 thin film.
[0019] Example 2
[0020] (1) Add 50 ml of distilled water and 25 ml of hydrochloric acid (36-38%) to a beaker and stir slowly for 10 min at a constant temperature of 25°C using a magnetic stirrer. Then, slowly add 0.75 ml of tetrabutyl titanate solution dropwise to the stirred mixture and stir slowly for another 10 min. Next, place the cleaned FTO at a 45° angle in the liner of a 25 ml reactor, with the conductive surface facing down. Then pour the prepared solution into the liner of the reactor and seal it. Perform a hydrothermal reaction in an electric heating drying oven at 160°C for 24 h, then cool and remove it, and dry it in a drying oven at 60°C to obtain a TiO2 film.
[0021] (2) 25 ml of anhydrous ethanol, 25 ml of diethylene glycol, 7.5 ml of isopropanol, and 35 ml of distilled water were added to a beaker sequentially and stirred slowly for 10 min at a constant temperature of 25 °C using a magnetic stirrer. Then, 0.9465 g of Ba(OH)₂·8H₂O solid particles and 0.326 g of Ce(NO₃)₃·6H₂O were added to the stirred solution, and the mixture was stirred slowly until all the solid particles dissolved. Next, the FTO containing the prepared TiO₂ was placed at a 45° angle in the liner of a 25 ml reactor, with the conductive surface facing down. The prepared solution was then poured into the liner of the reactor and sealed. The reactor was subjected to hydrothermal reaction in an electric heating drying oven at 200 °C for 6 h, then cooled and dried in a drying oven at 60 °C. Finally, it was calcined in a muffle furnace at 500 °C for 1 h to obtain highly crystalline Ba. 0.8 Ce 0.2 TiO3 thin film.
[0022] The present invention has been described in detail above through embodiments, but the content described is only an exemplary embodiment of the present invention and should not be considered as limiting the scope of the present invention. The scope of protection of the present invention is defined by the claims. Any technical solutions designed by those skilled in the art using the technical solutions described in the present invention, or similar technical solutions designed by those skilled in the art under the inspiration of the technical solutions of the present invention, within the substance and scope of protection of the present invention, to achieve the above-mentioned technical effects, or equivalent changes and improvements made to the scope of the application, should still fall within the patent protection scope of the present invention. It should be noted that, for clarity, descriptions of some components and processes that are not directly and obviously related to the scope of protection of the present invention but are known to those skilled in the art have been omitted in the description of the present invention.
Claims
1. A Ba for thermo-electro-photocatalysis 0.8 Ce 0.2 The method for preparing TiO3 thin film material is characterized by: The preparation method comprises the following steps performed in sequence: (1) Mix deionized water and hydrochloric acid in a 1:1 ratio until homogeneous, then slowly add a few drops of tetrabutyl titanate and stir at a certain temperature for a period of time until the solution becomes clear. Place the cleaned FTO conductive glass, conductive side down, on the inner wall of the reactor. After hydrothermal reaction at a certain temperature for a certain time, clean and dry the sample to obtain the TiO2 precursor. (2) Prepare a mixed solvent by adding diethylene glycol, isopropanol, and tetrabutylammonium hydroxide solution to deionized water. Dissolve barium hydroxide octahydrate, barium hydroxide hexahydrate, and cerium nitrate in the prepared solution in proportion. Perform in-situ conversion using a hydrothermal method, and then convert all TiO2 to doped Ba using a muffle furnace. 0.8 Ce 0.2 TiO3 thin film materials.
2. The Ba for thermo-photocatalysis according to claim 1 0.8 Ce 0.2 The method for preparing TiO3 thin film material is characterized by: In step (1), the volume of the tetrabutyl titanate is 0.500-1.000 ml, the temperature and time of the hydrothermal reaction are 160-180℃ and 18-24 h, respectively, and the product is dried in a drying oven for 2-4 h.
3. The Ba for thermo-photocatalysis according to claim 1 0.8 Ce 0.2 The method for preparing TiO3 thin film material is characterized by: In step (2), the concentration of barium hydroxide octahydrate is 0.500–1.000 mM, and the doping ratio of hexahydrate and cerium nitrate is 15–25%. TiO2 is converted to Ba in situ via a hydrothermal method. 0.8 Ce 0.2 TiO3 thin film materials.