CN112058252A - Hollow core-shell structure ZnO/In2O3Heterogeneous II type photocatalytic material and preparation method thereof - Google Patents
Hollow core-shell structure ZnO/In2O3Heterogeneous II type photocatalytic material and preparation method thereof Download PDFInfo
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- B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
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Abstract
Hollow core-shell structure ZnO/In2O3A heterogeneous II type photocatalytic material and a preparation method thereof, the method comprises the following steps: dissolving zinc salt and indium salt in a mixed solution of water, ethylene glycol and polyethylene glycol; step two: adding urea and sodium citrate into the solution obtained in the step one under stirring to obtain a reaction system mixed solution; step three: transferring the reaction system mixed solution obtained in the step two to a high-pressure reaction kettle for hydrothermal reaction; step four: cooling the hydrothermal reaction product obtained In the third step to room temperature, centrifuging, washing, drying and calcining to obtain ZnO/In with a hollow core-shell structure2O3Heterogeneous type II photocatalytic materials. The invention relates to aThe construction of the hollow shell-core structure and the heterogeneous II-type photocatalytic material can be realized simultaneously by a simple one-step hydrothermal method, and the nanoparticles prepared by the method have small particle size, so that the in-vivo recombination of carriers can be effectively inhibited, and the photocatalytic efficiency is improved.
Description
Technical Field
The invention relates to the technical field of preparation of photocatalytic materials, In particular to ZnO/In with a hollow core-shell structure2O3A heterogeneous II type photocatalytic material and a preparation method thereof.
Background
The rapid development of industry has led to a severe increase in environmental pollution, with organic pollutants being one of the major sources of pollution. The photocatalytic oxidation technology of these organic dye waste waters has received attention in recent years due to their high efficiency and low cost. ZnO has a high light absorption coefficient, a fast hole transport and an underwater stability, and thus has a wide energy band gap, and limits light absorption only in the UV region, and thus is widely used. In order to improve the photocatalytic efficiency of ZnO, it is important to suppress carrier recombination and improve the light utilization efficiency.
In recent years, a hollow shell material having a unique hollow structure has attracted much attention. The hollow sphere material has low relative density, high specific surface area, excellent packaging capacity, good permeability and excellent acoustic, optical, electric, magnetic and other properties, and is widely applied to the fields of drug carriers, biocatalysis, disease diagnosis, photoelectric devices and the like. The main preparation methods include template methods (soft template and hard template), hydrothermal synthesis methods, ultrasonic chemical methods, spray drying methods and the like. At present, carbon balls are mostly adopted, PS balls are used as hard templates, the templates are subsequently calcined to obtain hollow structures, the experimental process of the method is complex, and the balls are easy to collapse in the subsequent calcining process.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide ZnO/In with a hollow core-shell structure2O3The heterogeneous II type photocatalytic material and the preparation method thereof realize the construction of the hollow core-shell structure and the heterogeneous II type photocatalytic material simultaneously by a simple one-step hydrothermal method, andthe nano-particles prepared by the method have smaller particle size, and can effectively inhibit the in-vivo recombination of carriers, thereby improving the photocatalytic efficiency.
In order to achieve the purpose, the invention adopts the technical scheme that:
hollow core-shell structure ZnO/In2O3Heterogeneous type ii photocatalytic material, ZnO band edge: ECB-0.31 eV, EVB +2.89eV, In2O3Band edge: ECB-0.62 eV and EVB +2.181eV, which are matched to form ZnO/In2O3A heterogeneous type II photocatalytic system.
The ZnO and In2O3All present nanometer small particles.
The hollow core-shell structure ZnO/In2O3The heterogeneous II type photocatalytic material is a hollow double-layer spherical shell-core structure assembled by nano small particles.
Hollow core-shell structure ZnO/In2O3The preparation method of the heterogeneous II type photocatalytic material comprises the following steps:
the method comprises the following steps:
dissolving zinc salt and indium salt in a mixed solution of water, ethylene glycol and polyethylene glycol;
step two:
adding urea and sodium citrate into the solution obtained in the step one under stirring to obtain a reaction system mixed solution;
step three:
transferring the reaction system mixed solution obtained in the step two to a high-pressure reaction kettle for hydrothermal reaction;
step four:
cooling the hydrothermal reaction product obtained In the third step to room temperature, centrifuging, washing, drying and calcining to obtain ZnO/In with a hollow core-shell structure2O3Heterogeneous type II photocatalytic materials.
In the first step, the molar ratio of zinc salt to indium salt is 2: 1, and magnetically stirring at room temperature to prepare a mixed solution.
The zinc salt and the indium salt are respectively zinc nitrate and indium nitrate.
In the first step, the volume ratio of water, glycol and polyethylene glycol is 1 +/-0.5: 1: 1.
in the second step, the concentration of urea is 0.5 +/-0.05M, and the concentration of sodium citrate is 0.1 +/-0.05M.
The hydrothermal reaction temperature in the third step is 180-220 ℃, and the reaction time is 10-24 h.
In the fourth step, the centrifugal speed is 6000-8000 rpm, the centrifugal time is 8min, deionized water and ethanol are adopted for washing, and then drying is carried out for 600min at the temperature of 60 ℃.
In the fourth step, the calcining temperature is 400-500 ℃, the heating rate is 4 ℃/min, and the heat preservation time is 150-180 min.
The concentration ratio of urea to (indium salt + indium salt) is (3-12): 1.
the invention has the beneficial effects that:
one-step hydrothermal method is adopted to synthesize hollow core-shell structure ZnO/In2O3The heterogeneous II type photocatalytic material is free from adding redundant template agent, the method has the advantages of simple operation, easy equipment acquisition, environmental friendliness, low energy consumption and the like, and raw materials are cheap and easy to obtain and have low toxicity.
The ZnO selected In the invention has a suitable energy band edge (ECB ═ 0.31eV, EVB ═ 2.89eV), and can be reacted with In2O3Band edge: ECB-0.62 eV and EVB +2.181eV, which are matched to form ZnO/In2O3A heterogeneous type II photocatalytic system. The heterogeneous II-type photocatalytic system can not only fully utilize the photon-generated carriers of two materials, but also effectively inhibit the recombination of the photon-generated carriers, and simultaneously, the response range of light is also expanded.
The hollow shell-core structure can effectively enhance the reflection of light, thereby improving the utilization rate of a light source.
The spherical hollow shell-core structure constructed by the one-step template-free method has high surface area and pore size distribution, and is proved to be preferable in electrochemistry due to uniform pores and ordered mesoporous structures.
The hollow shell-core spherical structure prepared by the method is assembled by small nano particles, and a large number of pore canal pores exist among the assembled small particles, and the pore canal pores are beneficial to the directional movement of electrons, so that the photocatalysis efficiency of the material can be improved. See TEM image 4
Drawings
FIG. 1 shows the hollow core-shell structure ZnO/In prepared by the above steps2O3A photocatalysis mechanism diagram of heterogeneous II type photocatalysis material.
FIG. 2 shows the hollow core-shell structure ZnO/In prepared by the above steps2O3XRD spectrogram of heterogeneous II type photocatalytic material.
FIG. 3 shows the hollow core-shell structure ZnO/In prepared by the above steps2O3SEM image of heterogeneous type II photocatalytic material.
FIG. 4 shows the hollow core-shell structure ZnO/In prepared by the above steps2O3TEM image of heterogeneous type II photocatalytic material.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
In order to further understand the present invention, the following further describes the present invention with reference to specific embodiments, and the technical solutions in the embodiments of the present invention are clearly and completely described. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless otherwise specified, the reagents involved in the examples of the present invention are all commercially available products, and all of them are commercially available. Ethylene glycol (HOCH) for use in the present invention2CH2OH), polyethylene glycol (HO (CH)2CH2O)nH is analytically pure and purchased from national pharmaceutical chemicals, Inc.; indium nitrate hydrate (in (NO)3·4.5H2O), Zinc nitrate hydrate (Zn (NO)2·6H2O) were all purchased from makelin biochemical technologies, ltd.
Example 1: hollow core-shell structureForm ZnO/In2O3Preparation method of heterogeneous II type photocatalytic material
Weighing 0.59g of zinc nitrate and 0.38g of indium nitrate, stirring and dissolving in a mixed solution containing 20mL of ethylene glycol, 20mL of polyethylene glycol and 10mL of distilled water, adding 0.8g of sodium citrate and 1.5g of urea into the stirred mixed solution, stirring for 3h, transferring the stirred mixed solution into a high-pressure reaction kettle, carrying out hydrothermal reaction at 200 ℃ for 12h, centrifuging the product after hydrothermal reaction at 8000rpm for 8min, washing the centrifugate three times with distilled water, washing the centrifugate twice with alcohol, drying the washed centrifugate for 600min at 60 ℃, and calcining the dried sample in a tubular furnace at 500 ℃ for 180 min.
Example 2:
weighing 0.59g of zinc nitrate and 0.38g of indium nitrate, stirring and dissolving in a mixed solution containing 20mL of ethylene glycol, 20mL of polyethylene glycol and 10mL of distilled water, adding 0.9g of sodium citrate and 1.5g of urea into the stirred mixed solution, stirring for 3h, transferring the stirred mixed solution into a high-pressure reaction kettle, carrying out hydrothermal reaction at 200 ℃ for 12h, centrifuging the product after hydrothermal reaction at 8000rpm for 8min, washing the centrifugate three times with distilled water, washing the centrifugate twice with alcohol, drying the washed centrifugate for 600min at 60 ℃, and calcining the dried sample in a tubular furnace at 500 ℃ for 180 min.
Example 3:
weighing 0.59g of zinc nitrate and 0.38g of indium nitrate, stirring and dissolving in a mixed solution containing 20mL of ethylene glycol, 20mL of polyethylene glycol and 10mL of distilled water, adding 1.0g of sodium citrate and 1.5g of urea into the stirred mixed solution, stirring for 3h, transferring the stirred mixed solution into a high-pressure reaction kettle, carrying out hydrothermal reaction at 200 ℃ for 12h, centrifuging the product after hydrothermal reaction at 8000rpm for 8min, washing the centrifugate three times with distilled water, washing the centrifugate twice with alcohol, drying the washed centrifugate for 600min at 60 ℃, and calcining the dried sample in a tubular furnace at 500 ℃ for 180 min.
Example 4:
weighing 0.59g of zinc nitrate and 0.38g of indium nitrate, stirring and dissolving in a mixed solution containing 20mL of ethylene glycol, 20mL of polyethylene glycol and 10mL of distilled water, adding 1.0g of sodium citrate and 1.5g of urea into the stirred mixed solution, stirring for 3h, transferring the stirred mixed solution into a high-pressure reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 24h, centrifuging the product after hydrothermal reaction at 8000rpm for 8min, washing the centrifugate three times with distilled water, washing the centrifugate twice with alcohol, drying the washed centrifugate at 60 ℃ for 600min, and putting the dried sample into a tubular furnace, calcining the sample at 500 ℃ for 180 min.
Example 5:
weighing 0.59g of zinc nitrate and 0.38g of indium nitrate, stirring and dissolving in a mixed solution containing 20mL of ethylene glycol, 20mL of polyethylene glycol and 10mL of distilled water, adding 1.0g of sodium citrate and 1.5g of urea into the stirred mixed solution, stirring for 3h, transferring the stirred mixed solution into a high-pressure reaction kettle, carrying out hydrothermal reaction at 220 ℃ for 10h, centrifuging a product obtained after hydrothermal reaction at 6000rpm for 8min, washing a centrifugate with distilled water for three times, drying the product at 60 ℃ for 600min after washing the centrifugate with alcohol twice, and calcining the dried sample in a tubular furnace at 400 ℃ for 150 min.
Heterojunction photocatalysts composed of two or more semiconductors are currently being studied, thereby greatly improving photocatalytic efficiency. The charge transfer on the photocatalyst of the heterojunction structure has two possible mechanisms, namely a heterogeneous Z type and a heterogeneous II type, which depend on the direction of charge movement, wherein the heterogeneous II type photocatalytic system can not only make full use of photon-generated carriers of two materials, but also effectively inhibit the recombination of the photon-generated carriers, and the utilization rate of the heterogeneous II type carriers is higher than that of the heterogeneous Z type photocatalyst. The special spherical hollow core-shell structure is beneficial to multiple reflection and utilization of light, effectively improves the specific surface area and increases the reactive sites. As shown in fig. 1: under the excitation of light, the two materials generate carriers, and electrons are generated from In due to the difference of energy band structures2O3The conduction band of (A) is transferred to the conduction band of ZnO, and the corresponding hole is transferred from the valence band of ZnO to In2O3The valence band of (3) can sufficiently utilize the generated carriers and effectively suppress the recombination of the carriers.
As shown in fig. 2: it can be seen from the figure that it has good crystallinity. Indium salt with In2O3Oxides are present (PDF #06-0416), and the Zn salt forms conventional wurtzite ZnO (PDF # 36-1451).
As shown in fig. 3: the figure clearly shows that the synthesized catalytic material is in a regular spherical shape, and the broken spheres can show that the catalytic material has an obvious core-shell structure.
As shown in fig. 4: the spherical particles in the figure have clear hollow structures, and the generation of the core-shell structure can be seen through the difference of colors.
Claims (10)
1. Hollow core-shell structure ZnO/In2O3Heterogeneous II type photocatalytic material, its characterized in that, ZnO energy band edge: ECB-0.31 eV, EVB +2.89eV, In2O3Band edge: ECB-0.62 eV and EVB +2.181eV, which are matched to form ZnO/In2O3A heterogeneous type II photocatalytic system.
2. Hollow core-shell structure ZnO/In according to claim 12O3A heterogeneous II type photocatalytic material, characterized In that said ZnO and In2O3All present nanometer small particles.
3. Hollow core-shell structure ZnO/In according to claim 12O3A heterogeneous II type photocatalytic material is characterized in that,
the hollow core-shell structure ZnO/In2O3The heterogeneous II type photocatalytic material is a hollow double-layer spherical shell-core structure assembled by nano small particles.
4. ZnO/In with hollow core-shell structure based on claim 12O3The preparation method of the heterogeneous II type photocatalytic material is characterized by comprising the following steps:
the method comprises the following steps:
dissolving zinc salt and indium salt in a mixed solution of water, ethylene glycol and polyethylene glycol;
step two:
adding urea and sodium citrate into the solution obtained in the step one under stirring to obtain a reaction system mixed solution;
step three:
transferring the reaction system mixed solution obtained in the step two to a high-pressure reaction kettle for hydrothermal reaction;
step four:
cooling the hydrothermal reaction product obtained In the third step to room temperature, centrifuging, washing, drying and calcining to obtain ZnO/In with a hollow core-shell structure2O3Heterogeneous type II photocatalytic materials.
5. Hollow core-shell structure ZnO/In according to claim 42O3The preparation method of the heterogeneous II type photocatalytic material is characterized in that in the first step, the molar ratio of zinc salt to indium salt is 2: 1, and magnetically stirring at room temperature to prepare a mixed solution.
6. Hollow core-shell structure ZnO/In according to claim 42O3The preparation method of the heterogeneous II type photocatalytic material is characterized in that in the step one, the volume ratio of water, glycol and polyethylene glycol is 1 +/-0.5: 1: 1.
7. hollow core-shell structure ZnO/In according to claim 42O3The preparation method of the heterogeneous II type photocatalytic material is characterized in that in the second step, the concentration of urea is 0.5 +/-0.05M, the concentration of sodium citrate is 0.1 +/-0.05M, and the concentration ratio of urea to (indium salt + indium salt) is (3-12): 1.
8. hollow core-shell structure ZnO/In according to claim 42O3The preparation method of the heterogeneous II type photocatalytic material is characterized in that the hydrothermal reaction temperature in the third step is 180-220 ℃, and the reaction time is 10-24 h.
9. Hollow core-shell structure ZnO/In according to claim 42O3The preparation method of the heterogeneous II type photocatalytic material is characterized in that in the fourth step, the centrifugal speed is 6000-8000 rpm, the centrifugal time is 8min, deionized water and ethanol are adopted for washing, and then drying is carried out for 600min at the temperature of 60 ℃.
10. Hollow core-shell structure ZnO/In according to claim 42O3The preparation method of the heterogeneous II type photocatalytic material is characterized in that in the fourth step, the calcination temperature is 400-500 ℃, the heating rate is 4 ℃/min, and the heat preservation time is 150-180 min.
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Cited By (5)
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| CN117026004A (en) * | 2023-08-31 | 2023-11-10 | 昆明理工大学 | ZnO@In 2 O 3 Reinforced silver-based composite material and preparation method thereof |
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