CN103877966B - A kind of preparation method of heterojunction structure photochemical catalyst - Google Patents
A kind of preparation method of heterojunction structure photochemical catalyst Download PDFInfo
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- CN103877966B CN103877966B CN201410139856.7A CN201410139856A CN103877966B CN 103877966 B CN103877966 B CN 103877966B CN 201410139856 A CN201410139856 A CN 201410139856A CN 103877966 B CN103877966 B CN 103877966B
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Abstract
A preparation method for heterojunction structure photochemical catalyst, relates to environmental technology field, also relates to the preparing technical field of catalyst in photocatalysis technology field.By NaOH, urea and SnCl
22H
2o is dissolved in ethanol water, forms mixed solution, reacts under the temperature of mixed solution is the condition of 180 DEG C; After having reacted, mixed system is cooled to normal temperature, taking precipitate deionized water and the cleaning of absolute ethyl alcohol alternating centrifugal, dry.SnO and Sn in the product of the present invention's synthesis
3o
4two kinds of heterojunction structure products are also deposited, and define hollow flower-shaped, and have larger specific area and hollow bobbles structure, have very high efficiency of light absorption, photocatalysis performance is high, and properties of catalyst stablizes non-secondary pollution.
Description
Technical field
The present invention relates to environmental technology field, also relate to the preparing technical field of catalyst in photocatalysis technology field.
Background technology
Along with the development of industrial or agricultural, the environmental problems such as water pollutions make research and the preparation of people's extensive concern light degradation contaminant material.Tin oxygen compound (SnO
2(Eg=3.5eVatRT) and SnO (Eg=2.7eVatRT)) due to its mature preparation process, in alkalescence and acid solution under illumination steady performance in photocatalysis extensive application.But due to its SnO
2and SnO belongs to wide bandgap semiconductor, be only limited to and realize photocatalysis performance under ultraviolet light.Simple use SnO
2and SnO is very limited in actual use as photochemical catalyst.
Improve tin oxygen compound photocatalysis performance main stream approach to have: carry out control to increase its efficiency of light absorption and light-catalyzed reaction area to pattern and size; Photocatalysis under improving photocatalysis performance by introducing low-gap semiconductor formation hetero-junctions and realize visible ray, according to heterogeneous band structure feature, wherein
type heterogeneous semiconductor is owing to can realize the preferred material being effectively separated into heterogeneous photochemical catalyst of photo-generated carrier to a great extent.Although above main stream approach improves the photocatalysis performance of semiconductor to a certain extent, but still there is the problems such as such as complex steps, products therefrom amount are little, cost intensive, thus also limit the application at industrial circle.
Sn
3o
4homologous series oxide as tin-based oxide belongs to low-gap semiconductor due to it, and up to the present SnO/Sn is prepared in experimentally preparation
3o
4also there is not report.The present invention successfully achieves SnO/Sn by traditional one step hydro thermal method first experimentally
3o
4prepared by low cost, and this SnO/Sn
3o
4iI type heterojunction structure is expected to realize excellent photocatalysis performance under visible light.
Summary of the invention
The present invention seeks to preparation one and be beneficial to reduction production cost, there is the preparation method of the heterojunction structure photochemical catalyst of higher photocatalysis performance.
The present invention includes following steps:
1) by NaOH, urea and SnCl
22H
2o is dissolved in ethanol water, forms mixed solution;
2) mixed solution is placed in reactor, reacts under the temperature of mixed solution is the condition of 180 DEG C;
3) after having reacted, mixed system is cooled to normal temperature, taking precipitate deionized water and the cleaning of absolute ethyl alcohol alternating centrifugal, get solids at 60 DEG C after drying, take out product.
The invention has the advantages that SnO and Sn in the product of synthesis
3o
4two kinds of heterojunction structure products are also deposited, and define hollow flower-shaped, and have larger specific area and hollow bobbles structure, have very high efficiency of light absorption, photocatalysis performance is high, and properties of catalyst stablizes non-secondary pollution.The inventive method, one-step synthesis, synthesis temperature is low, and preparation technology is simple, and the required raw material of preparation are cheap, and synthetic quantity is large, solves traditional photochemical catalyst two step or multistep synthesis and the high problem of preparation cost, can promote and be applied to industrial circle.
In addition, consider the suitable viscosity of precursor aqueous solution, the ethanol mass percent of ethanol water of the present invention is 60%.
Consider the flower-like nanostructure preparing bigger serface and excellent absorbing properties, NaOH of the present invention, urea and SnCl
22H
2the mass ratio that feeds intake of O is 1.2:1:565.
In described NaOH and ethanol water, the rate of charge of ethanol is 4g:75ml.
Accompanying drawing explanation
The SnO/Sn with high photocatalysis performance of Fig. 1 prepared by example of the present invention
3o
4the x-ray diffraction pattern of II type heterojunction structure.
The SnO/Sn with high photocatalysis performance of Fig. 2 prepared by example of the present invention
3o
4the stereoscan photograph figure of II type heterojunction structure.
The SnO/Sn with high photocatalysis performance of Fig. 3 prepared by example of the present invention
3o
4the transmission electron microscope of II type heterojunction structure and SEAD figure.
The SnO/Sn of the photocatalysis performance of Fig. 4 prepared by example of the present invention
3o
4the UV-Vis absorption properties of II type heterogeneous structure material and the band structure of hetero-junctions calculated thus.
The SnO/Sn with high photocatalysis performance prepared by Fig. 5 example of the present invention
3o
4the photocatalysis performance figure of II type heterojunction structure.
Detailed description of the invention
One, heterojunction structure photochemical catalyst is prepared:
Choose NaOH powder (3.84g, 99.99%, Sigma-Aldrich), urea powder (3.2g, 99.999%, Sigma-Aldrich), SnCl
22H
2o powder (1,808g, 99.999%, Sigma-Aldrich) is dissolved in the mixed solution of the absolute ethyl alcohol of 140ml deionized water and 60ml.Stir after 2 hours, mixed solution is placed in 200ml reactor, hydro-thermal reaction 18 hours at 180 DEG C; Then reactor to be taken out under cold water fast cooling 0.5 hour, afterwards by gained sediment deionized water and the cleaning of absolute ethyl alcohol alternating centrifugal, and by products therefrom at 60 DEG C dry 12 hours, finally take out product.
Two, verify:
As shown in Fig. 1, Fig. 2, Fig. 3, Fig. 4, D8ADVANCE type XRD (Curadiation, German Bruker-AXS company) is adopted to measure the crystal phase structure of prepared sample.Adopt Hitachi, Ltd (Japan) S4800
type FESEM (FESEM, s-4800
, Hitachi) pattern of prepared sample is observed.The TecnaiF30 Flied emission transmission electron microscope (HRTEM, TecnaiF30, FEI) of Dutch philips-FEI company is adopted to detect intuitively the crystal phase structure of sample and characterize.Cary5000 type UV-visible-near infrared absorption instrument (Varian company of the U.S.) is adopted to analyze the UV-Vis absorption properties of sample and band structure.XPA-7 type photochemical reaction instrument (Xujiang Electromechanical Plant, Nanjing, China) and UV-3600 type spectrometer (Japanese Shimadzu Corporation) is adopted to carry out the photocatalysis performance test of RhB dye degrades to gained sample.
Result of the test shows:
Fig. 1: the SnO/Sn of the photocatalysis performance prepared by example of the present invention
3o
4the x-ray diffraction pattern of II type heterojunction structure, in Fig. 1, the illustration of right corner is the high magnification XRD of 22 ~ 35 °.All diffraction maximums shown in master map from left to right correspond respectively to (001) of four direction SnO, (101), (002), (112), (103).Diffraction maximum from left to right shown in illustration corresponds respectively to anorthic system Sn
3o
4(101), (-120), (111), (-210), (-121), (210).Diagram XRD describes SnO and Sn in prepared sample
3o
4coexist.
Fig. 2: the SnO/Sn of the photocatalysis performance prepared by example of the present invention
3o
4scanning/transmission electron microscope photo the figure of II type heterojunction structure.As can be seen from scanning electron microscope (SEM) photograph, the inventive method successfully realizes the flower-like nanometer ball evenly prepared in large area, from transmission electron microscope illustration, diameter greatly about about 5 μm, and it can also be seen that the flower-like nanometer ball prepared presents hollow-core construction.This pattern has large specific area and hollow-core construction increases its efficiency of light absorption and light-catalyzed reaction area to a great extent, is conducive to the raising of photocatalysis performance.
Fig. 3: the SnO/Sn of the photocatalysis performance prepared by example of the present invention
3o
4the high power transmission electron microscope of II type heterogeneous structure material and SEAD figure.The SnO/Sn with high photocatalysis performance prepared by example can be found out from the transmission electron microscope of high power and SEAD
3o
4iI type heterogeneous structure material is by SnO and Sn
3o
4form.Wherein 0.192nm corresponds to (102 crystal face) of SnO, and 0.315nm corresponds to Sn
3o
4(111) face.
Fig. 4: the SnO/Sn of the photocatalysis performance prepared by example of the present invention
3o
4the UV-Vis absorption properties of II type heterogeneous structure material and the band structure of hetero-junctions calculated thus.From SnO/Sn
3o
4the band structure analysis of heterojunction structure can be found out: SnO and Sn
3o
4valence band and conduction band interlaced, belong to II type semiconductor heterostructure.SnO and Sn is it can also be seen that in figure
3o
4belong to low-gap semiconductor (SnO (Eg=2.47eVatRT) and Sn
3o
4(Eg=2.19eVatRT), this SnO/Sn
3o
4iI type heterojunction structure is expected to realize excellent photocatalysis performance under visible light.
Fig. 5: the SnO/Sn with high photocatalysis performance prepared by example of the present invention
3o
4iI type heterojunction structure photocatalysis performance figure.As can be seen from Fig., the SnO/Sn synthesized by the present invention
3o
4the concentration of original dyestuff just can be reduced to less than 8% at about about 90 minutes by II type heterogeneous structure material.
According to above-mentioned result of study: the SnO/Sn of prepared by the present invention have high photocatalysis performance
3o
4the material preparation procedure of II type heterojunction structure is simple, with low cost, and synthetic quantity is large, and is expected to realize good photo-catalysis capability under visible light.
Therefore, as can be seen from above-mentioned experimental procedure, data and graphic analyses, the present invention synthesizes the SnO/Sn with high photocatalysis performance first
3o
4iI type heterogeneous structure material, and preparation process is simple, with low cost, be suitable for commercial Application.
Claims (3)
1. a preparation method for heterojunction structure photochemical catalyst, is characterized in that comprising the following steps:
1) by NaOH, urea and SnCl
22H
2o is dissolved in ethanol water, forms mixed solution; Described NaOH, urea and SnCl
22H
2the mass ratio that feeds intake of O is 1.2:1:0.565;
2) mixed solution is placed in reactor, under the temperature of mixed solution is the condition of 180 DEG C, carries out reaction 18 hours;
3) after having reacted, mixed system is cooled to normal temperature, taking precipitate deionized water and the cleaning of absolute ethyl alcohol alternating centrifugal, get solids at 60 DEG C after drying, take out product.
2. preparation method according to claim 1, is characterized in that the ethanol mass percent of described ethanol water is 60%.
3. preparation method according to claim 1 or 2, is characterized in that the rate of charge of ethanol in described NaOH and ethanol water is 4g:75ml.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107670657A (en) * | 2017-10-16 | 2018-02-09 | 陕西科技大学 | A kind of Zn2SnO4@C photochemical catalysts and preparation method thereof |
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| CN105036068B (en) * | 2015-06-17 | 2016-06-22 | 山东大学 | A kind of composite being suitable to low temperature alcohol sensor and application thereof |
| CN106000384B (en) * | 2016-05-13 | 2018-04-10 | 淮北师范大学 | A kind of preparation method and its photocatalytic applications for forming controllable tin-based oxide |
| CN105895890A (en) * | 2016-06-06 | 2016-08-24 | 西北工业大学 | Application of Sn3O4 solar catalyst in negative electrode material of lithium ion battery |
| CN107445196A (en) * | 2017-05-25 | 2017-12-08 | 南京工业大学 | A kind of stratiform Sn3O4/SnO2The preparation method of hetero-junctions square piece type gas sensitive |
| JP6946984B2 (en) * | 2017-12-01 | 2021-10-13 | 三菱マテリアル株式会社 | Photocatalyst manufacturing method |
| CN109360952A (en) * | 2018-09-25 | 2019-02-19 | 陕西科技大学 | A kind of preparation method of nanometer sheet structure tin oxide/tetra- three tin lithium ion battery negative materials of oxidation |
| CN110064386B (en) * | 2019-05-30 | 2021-08-24 | 济南大学 | Tin nanoparticle modified composite photocatalytic material with oxygen vacancy stannic oxide nanosheets and preparation method thereof |
| CN110668416B (en) * | 2019-10-08 | 2023-06-27 | 扬州大学 | Photocatalytic reduction of CO 2 Is a method of (2) |
| CN114405497A (en) * | 2022-01-21 | 2022-04-29 | 辽宁大学 | Three-dimensional flower-shaped Bi @ Sn3O4Schottky junction visible light catalyst and preparation method and application thereof |
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| JP2004214493A (en) * | 2003-01-07 | 2004-07-29 | Yaskawa Electric Corp | Apparatus for forming gate oxide film |
| CN102145916B (en) * | 2011-03-28 | 2012-11-28 | 宁波大学 | Preparation method of Sn3O4 nano powder |
| CN102723207A (en) * | 2012-05-31 | 2012-10-10 | 南京大学昆山创新研究院 | Preparation method and purpose of Zn mixed SnO2 ball with mesoporous micro/nano hierarchical structure |
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| CN107670657A (en) * | 2017-10-16 | 2018-02-09 | 陕西科技大学 | A kind of Zn2SnO4@C photochemical catalysts and preparation method thereof |
| CN107670657B (en) * | 2017-10-16 | 2020-05-05 | 陕西科技大学 | Zn2SnO4@ C photocatalyst and preparation method thereof |
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