Glucose carbonization synergistically modified SrTiO3 photocatalyst as well as preparation method and application thereof
By modifying SrTiO3 photocatalyst with glucose carbonization, the photoresponse range was broadened and the carrier separation efficiency was improved, thus overcoming the bottleneck of pure-phase SrTiO3 photocatalytic performance and achieving a highly efficient photocatalytic water splitting effect.
Patent Information
- Application Number
- CN202610092420.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-01-23
- Publication Date
- 2026-04-24
AI Technical Summary
Pure-phase SrTiO3 has a wide band gap, responds only to ultraviolet light, and its photogenerated electron-hole pairs recombine easily, resulting in low carrier separation efficiency and limiting the improvement of its photocatalytic performance.
By modifying SrTiO3 with glucose carbonization, in-situ doping and surface coating of carbon are achieved, which broadens the photoresponse range and improves the carrier separation efficiency, thus preparing SrTiO3 photocatalysts with glucose carbonization synergistic modification.
It expands the light response range into the visible light region, improves carrier separation efficiency and quantum yield, enhances the active sites of the catalyst, and significantly improves the efficiency of photocatalytic water splitting.
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Figure CN121911389A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of photocatalytic materials technology, specifically relating to a method for preparing and applying a glucose carbonization-synergistic modified SrTiO3 photocatalyst. Background Technology
[0002] In recent years, the global energy crisis and environmental degradation have become increasingly severe, making the development of clean and renewable new energy technologies a critical issue that urgently needs to be addressed. Solar energy, as the most abundant clean energy source, has its efficient conversion and utilization being one of the core research directions in the field of new energy. Photocatalytic water splitting for hydrogen production can directly convert solar energy into hydrogen energy, possessing both cleanliness and sustainability, and is considered an ideal way to solve the dual challenges of energy and the environment. Developing high-performance, highly stable photocatalytic materials is a core prerequisite for promoting the practical application of this technology.
[0003] Among numerous photocatalytic materials, perovskite oxide SrTiO3, with its stable ABO3 crystal structure, excellent chemical stability, and suitable band structure, has shown significant application potential in the field of photocatalytic water splitting. However, pure-phase SrTiO3 suffers from two inherent defects that severely restrict the improvement of its photocatalytic performance: First, the intrinsic band gap of SrTiO3 is approximately 3.2 eV, which only responds to the ultraviolet light region, which accounts for less than 4% of the solar spectrum, resulting in extremely low solar energy utilization; second, the photogenerated electron-hole pairs generated by photoexcitation in SrTiO3 recombine very quickly, leading to low carrier separation efficiency and difficulty in improving quantum yield.
[0004] To address the aforementioned bottlenecks, researchers have proposed various modification strategies, including ion doping, semiconductor composites, and surface-supported co-catalysts. Among these, carbon-based material modification has attracted significant attention due to its low cost and remarkable effects. Glucose, as a widely available and environmentally friendly biomass carbon source, has pyrolysis products with abundant functional groups and good electrical conductivity, making it an ideal precursor for modification.
[0005] Therefore, developing a simple, green, and environmentally friendly method for preparing SrTiO3 through glucose carbonization synergistic modification, achieving in-situ carbon doping and surface coating through low-temperature calcination, and simultaneously broadening the photoresponse range of SrTiO3, improving carrier separation efficiency, and optimizing surface reaction kinetics, is of great practical significance and application value for overcoming the performance bottleneck of pure-phase SrTiO3 and promoting the development of photocatalytic water splitting technology. Summary of the Invention
[0006] To address the above problems, this invention provides a glucose carbonization-synergistic modified SrTiO3 photocatalyst, its preparation method, and its application.
[0007] The technical solution adopted in this invention is as follows:
[0008] A glucose carbonization synergistic modification of SrTiO3 photocatalyst, wherein the glucose content is 0.8-1.2% of SrTiO3 by molar percentage.
[0009] A method for preparing a glucose carbonization-synergistic modified SrTiO3 photocatalyst includes the following steps:
[0010] 1) After mixing and grinding SrTiO3 and SrCl2·6H2O in a mortar, the mixture was transferred to an Al2O3 crucible, calcined in a muffle furnace, filtered and dried to obtain SrTiO3 nanoparticles.
[0011] 2) Weigh SrTiO3 nanoparticles and glucose, place them in a mortar, grind them evenly, calcine them in a muffle furnace, cool the calcined powder, place it in a beaker, add 30 mL of water, stir, filter and dry to obtain a glucose carbonization synergistic modified SrTiO3 photocatalyst.
[0012] Furthermore, in the above preparation method, in step 1), the mass ratio of SrTiO3 to SrCl2·6H2O is 1:14.5.
[0013] Furthermore, in the above preparation method, in step 1), the calcination temperature is 1100 ℃ and the calcination time is 10 h.
[0014] Furthermore, in the above preparation method, in step 2), the glucose content is 0.8%, 1%, or 1.2% of SrTiO3 by molar percentage.
[0015] Furthermore, in the above preparation method, in steps 1) and 2), the drying temperature is 60 ℃ and the drying time is 12 h.
[0016] Furthermore, in the above preparation method, step 2), the grinding time is 10 min.
[0017] Furthermore, in the above preparation method, step 2), the calcination temperature is 500 ℃, the heating rate is 5 ℃ / min, and the calcination time is 2 h.
[0018] The above-mentioned glucose carbonization-synergistic modified SrTiO3 photocatalyst is applied to the catalytic hydrolysis of water under visible light irradiation.
[0019] Further, the above application is carried out as follows: The photocatalyst is uniformly dispersed in a reaction vessel containing 20 ml of deionized water. The co-catalyst is photodeposited in situ. 126 μL of Na3RhCl6·12H2O aqueous solution with a concentration of 0.59 mg / mL is added, and the mass of Rh is 0.1% of SrTiO3. The mixture is irradiated with a 300 W xenon lamp for 10 min. Then, 10 μL of Cr(NO3)·9H2O aqueous solution with a concentration of 7.7 mg / mL is added, and the mass of Cr is 0.05% of SrTiO3. The mixture is irradiated with a 300 W xenon lamp for 5 min. Then, 21 μL of CoCl2·6H2O aqueous solution with a concentration of 10 mg / mL is added, and the mass of Co is 0.05% of SrTiO3. The mixture is irradiated with a 300 W xenon lamp for 5 min. Finally, the mixture is irradiated for another 5 min. Argon gas is continuously introduced into the container containing the mixed solution at a rate of 40 mL / min to create a relative vacuum environment. Under xenon lamp irradiation, water is decomposed and hydrogen is produced.
[0020] The beneficial effects of this invention are:
[0021] 1. This invention achieves in-situ doping and surface coating dual modification of carbon in glucose pyrolysis through calcination at 500℃. On the one hand, carbon atoms can partially embed into the interstitial spaces of SrTiO3 lattice or replace lattice oxygen sites, introducing impurity energy levels into the SrTiO3 bandgap, narrowing the originally wide bandgap of about 3.2 eV, and extending the photoresponse range from the ultraviolet region to the visible light region; on the other hand, the amorphous carbon layer loaded on the SrTiO3 surface has broad-spectrum absorption characteristics, which can capture visible and near-infrared light and provide charge carriers for catalytic reactions through photoinduced electron transfer mechanism.
[0022] 2. The core drawback of pure-phase SrTiO3 is its rapid photogenerated electron-hole recombination rate, leading to low quantum efficiency. In this invention, SrTiO3 forms a heterojunction interface with the carbon-based component. The Fermi level of carbon is lower than the conduction band bottom of SrTiO3. The built-in electric field formed at the interface can drive photogenerated electrons to migrate rapidly from the SrTiO3 conduction band to the carbon layer surface. At the same time, the carbon layer has excellent electron conductivity, which can serve as an electron transport channel to accelerate carrier migration to the reaction site, significantly suppressing bulk and surface recombination of electrons and holes, and significantly improving carrier separation efficiency and quantum yield.
[0023] 3. The carbon layer surface of glucose pyrolysis is rich in oxygen-containing functional groups such as hydroxyl and carboxyl groups. These functional groups can serve as additional catalytic active sites, enhancing the adsorption and activation of water molecules and lowering the reaction energy barriers for hydrogen evolution and oxygen evolution reactions. Simultaneously, the carbon layer coating increases the specific surface area of the catalyst, fully exposing the intrinsic active sites of the SrTiO3 matrix, further accelerating the surface redox reaction process. The method for preparing this catalyst is simple, convenient, low-cost, and operates under mild conditions, making it suitable for large-scale production. Attached Figure Description
[0024] Figure 1 shows the X-ray diffraction patterns of the SrTiO3 catalyst prepared in Example 1, the 0.8% C-SrTiO3 catalyst prepared in Example 2, the 1% C-SrTiO3 photocatalyst prepared in Example 3, and the 1.2% C-SrTiO3 catalyst prepared in Example 4.
[0025] Figure 2 The hydrogen and oxygen rates are shown in the graph for the 1% C-SrTiO3 photocatalyst prepared in Example 3.
[0026] Figure 3 is a comparison of the hydrogen evolution activities of the SrTiO3 catalyst prepared in Example 1, the 0.8% C-SrTiO3 catalyst prepared in Example 2, the 1% C-SrTiO3 photocatalyst prepared in Example 3, and the 1.2% C-SrTiO3 catalyst prepared in Example 4. Detailed Implementation
[0027] Example 1
[0028] The preparation method of SrTiO3 catalyst is as follows:
[0029] Weigh 14.5 g of SrCl2·6H2O and 1 g of commercially available SrTiO3 and place them in a mortar. Grind them for 30 min to make them evenly mixed. Then place them in an Al2O3 crucible and calcine them in a muffle furnace at 1100 ℃ for 10 h. Filter them and then dry them in an oven at 60 ℃ for 12 h to obtain SrTiO3 nanoparticles, denoted as STO.
[0030] Example 2
[0031] The preparation method of 0.8% C-SrTiO3 catalyst is as follows:
[0032] 0.183 g of SrTiO3 nanoparticles prepared in Example 1 and 0.00144 g of glucose were placed in a mortar and ground for 30 min to mix them evenly. The ground powder was placed in a porcelain boat and calcined in a muffle furnace at 500 °C (heating rate of 5 °C / min) for 3 h. After the calcined powder was cooled, it was placed in a beaker, 30 mL of water was added, stirred, filtered, and dried at 60 °C for 12 h to obtain 0.8% C-SrTiO3 photocatalyst, denoted as 0.8% C-STO.
[0033] Example 3
[0034] The preparation method of 1% C-SrTiO3 catalyst is as follows:
[0035] 0.183 g of SrTiO3 nanoparticles prepared in Example 1 and 0.0080 g of glucose were placed in a mortar and ground for 30 min to mix them evenly. The ground powder was placed in a porcelain boat and calcined in a muffle furnace at 500 °C (heating rate of 5 °C / min) for 3 h. After the calcined powder was cooled, it was placed in a beaker, 30 mL of water was added, stirred, filtered, and dried at 60 °C for 12 h to obtain 1% C-SrTiO3 photocatalyst, denoted as 1% C-STO.
[0036] Example 4
[0037] The preparation method of 1.2% C-SrTiO3 catalyst is as follows:
[0038] 0.183 g of SrTiO3 nanoparticles prepared in Example 1 and 0.00216 g of glucose were placed in a mortar and ground for 30 min to mix them evenly. The ground powder was placed in a porcelain boat and calcined in a muffle furnace at 500 °C (heating rate of 5 °C / min) for 3 h. After the calcined powder was cooled, it was placed in a beaker, 30 mL of water was added, stirred, filtered, and dried at 60 °C for 12 h to obtain a 1.2% C-SrTiO3 photocatalyst, denoted as 1.2% C-STO.
[0039] Example 5
[0040] Application of C-SrTiO3 photocatalyst in the catalytic hydrolysis of water under light irradiation:
[0041] 1) Under normal temperature and pressure conditions, 20 mg of SrTiO3 photocatalyst prepared in Example 1 was uniformly dispersed in a reaction vessel containing 20 mL of deionized water. The following three in-situ photodeposition co-catalysts were added: 126 μL of a 0.59 mg / mL Na3RhCl6·12H2O aqueous solution (Rh mass = 0.1% of SrTiO3 mass), irradiated with a 300 W xenon lamp for 10 min; 10 μL of a 7.7 mg / mL Cr(NO3)·9H2O aqueous solution (Cr mass = 0.05% of SrTiO3 mass), irradiated with a 300 W xenon lamp for 5 min; 21 μL of a 10 mg / mL CoCl2·6H2O aqueous solution (Co mass = 0.05% of SrTiO3 mass), irradiated with a 300 W xenon lamp for 5 min; and finally, irradiated for another 5 min. A relative vacuum environment was created by continuously introducing argon gas at a rate of 40 mL / min into the container containing the mixed solution. Under visible light irradiation conditions, the reaction was repeated every 30 minutes. A 1000 μL volume of gas was taken from the container using a microsyringe, and the collected catalytic products were quantitatively analyzed using a gas chromatograph.
[0042] 2) Following step 1), except that the SrTiO3 photocatalyst prepared in Example 1 was replaced with the 0.8% C-SrTiO3 catalyst prepared in Example 2, the 1% C-SrTiO3 catalyst prepared in Example 3, and the 1.2% C-SrTiO3 prepared in Example 4, all other conditions remained unchanged. The gas was then taken and the hydrogen and oxygen production efficiencies were measured.
[0043] Figure 1 X-ray diffraction patterns of the photocatalysts prepared for the above examples are shown. The characteristic signal peaks in the figure correspond to the (100), (110), (111), (200), (210), (211), (220), (300), and (310) crystal planes, which is consistent with the SrTiO3 PDF standard card (PDF#84-0443). This indicates that after in-situ carbon doping and surface coating modification, the crystal phase of SrTiO3 has not changed and still satisfies the photocatalytic water splitting requirement.
[0044] Figure 2 The graph shows the hydrogen and oxygen evolution rates of the 0.8%–1.2% C-SrTiO3 photocatalyst prepared in Example 3. The results show that within 2 hours, the highest hydrogen yield of 1% C-SrTiO3 was 0.77 mmol, and the highest oxygen yield was 0.36 mmol, with a hydrogen-to-oxygen ratio of approximately 2:1, which is 1.5 times the hydrogen yield of SrTiO3 within 2 hours (0.51 mmol). This indicates that glucose carbonization co-doping of SrTiO3 improves the separation efficiency of semiconductor photogenerated carriers, which is beneficial for improving the photocatalytic water splitting activity.
[0045] Figure 3 The image shows a comparison of the water splitting and hydrogen evolution activities of the SrTiO3, 0.8%C-SrTiO3, 1%C-SrTiO3, and 1.2%C-SrTiO3 photocatalysts prepared in Examples 1, 2, 3, and 4. Figure 3 As can be seen, after 1 h of photocatalysis, the H2 production of SrTiO3 was 13.15 mmol / g / h, that of 0.8% S-SrTiO3 was 18.03 mmol / g / h, that of 1% S-SrTiO3 was 20.06 mmol / g / h, and that of 1.2% S-SrTiO3 was 17.71 mmol / g / h. The modified photocatalysts showed a significant improvement in hydrogen production performance compared to pure SrTiO3. After in-situ doping and surface coating of the carbon from glucose pyrolysis, the carbon layer exhibited excellent electronic conductivity, serving as an electron transport channel to accelerate carrier migration to the reaction site, significantly suppressing bulk and surface recombination of electrons and holes, and substantially improving carrier separation efficiency and quantum yield.
Claims
1. A glucose carbonization-synergistic modified SrTiO3 photocatalyst, characterized in that, The glucose carbonization synergistic modification of the SrTiO3 photocatalyst has a glucose content of 0.8% to 1.2% of SrTiO3 by molar percentage.
2. The preparation method of the glucose carbonization synergistic modification SrTiO3 photocatalyst according to claim 1, characterized in that, Includes the following steps: Step 1: SrTiO3 and SrCl2·6H2O are mixed and ground in a mortar, then transferred to a crucible, calcined in a muffle furnace, filtered and dried to obtain SrTiO3 nanoparticles. Step 2: Weigh SrTiO3 nanoparticles and glucose, place them in a mortar, grind them evenly, calcine them in a muffle furnace, cool the calcined powder, add water, stir, filter and dry to obtain glucose carbonization synergistic modification of SrTiO3 photocatalyst.
3. The preparation method according to claim 2, characterized in that, In step 1, the mass ratio of SrTiO3 to SrCl2·6H2O is 1:14.
5.
4. The preparation method according to claim 2, characterized in that, In step 1, the calcination temperature is 1100 ℃ and the calcination time is 10 h.
5. The preparation method according to claim 2, characterized in that, In step 2, the glucose content is 0.8%~1.2% of SrTiO3 by molar percentage.
6. The preparation method according to claim 2, characterized in that, In steps 1 and 2, the drying temperature is 60°C and the drying time is 12 hours.
7. The preparation method according to claim 2, characterized in that, In step 2, the grinding time is 30 minutes.
8. The preparation method according to claim 2, characterized in that, In step 2, the calcination temperature is 500 ℃, the heating rate is 5 ℃ / min, and the calcination time is 3 h.
9. The application of the glucose carbonization-synergistic modified SrTiO3 photocatalyst according to claim 1 in the catalytic hydrolysis of water under visible light irradiation.
10. The application according to claim 9, characterized in that, The method is as follows: The prepared photocatalyst is uniformly dispersed in a reaction vessel containing deionized water. The following in-situ photodeposition co-catalysts are added: 126 μL of Na3RhCl6·12H2O aqueous solution with a concentration of 0.59 mg / mL is added, where Rh is 0.1% of SrTiO3. The mixture is irradiated with a 300 W xenon lamp for 10 min. Then, 10 μL of Cr(NO3)·9H2O aqueous solution with a concentration of 7.7 mg / mL is added, where Cr is 0.05% of SrTiO3. The mixture is irradiated with a 300 W xenon lamp for 5 min. Finally, 21 μL of CoCl2·6H2O aqueous solution with a concentration of 10 mg / mL is added, where Co is 0.05% of SrTiO3. The mixture is irradiated with a 300 W xenon lamp for 5 min. Finally, the mixture is irradiated for another 5 min. Argon gas is continuously introduced into the container containing the mixed solution at a rate of 40 mL / min to create a relative vacuum environment. Hydrogen is then generated by decomposing water under visible light irradiation.