CN103877966A - Preparation method of heterostructure photocatalyst - Google Patents
Preparation method of heterostructure photocatalyst Download PDFInfo
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- CN103877966A CN103877966A CN201410139856.7A CN201410139856A CN103877966A CN 103877966 A CN103877966 A CN 103877966A CN 201410139856 A CN201410139856 A CN 201410139856A CN 103877966 A CN103877966 A CN 103877966A
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Abstract
The invention discloses a preparation method of a heterostructure photocatalyst and relates to the technical field of environmental protection and preparation of catalysts in the technical field of photocatalysis. The method comprises the following steps: dissolving NaOH, urea and SnCl2.2H2O in an ethanol water solution to form a mixed solution, and reacting under the condition that the temperature of the mixed solution is 180 DEG C; after the reaction is finished, cooling a mixing system to the normal temperature, alternately performing centrifugal washing on deposits by using de-ionized water and absolute ethanol, and drying. According to the method, two heterostructures, SnO and Sn3O4, are coexistent in a synthetic product, a hollow flower shape is formed, the specific surface area and a hollow pompon structure are relatively high, the light absorption efficiency is very high, the photocatalytic performance is high and stable, and the secondary pollution is avoided.
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 pollution make research and the preparation of people's extensive concern light degradation contaminant material.Tin oxygen compound (SnO
2(Eg=3.5eV at RT) and SnO (Eg=2.7eV at RT)) 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 under ultraviolet light and realize photocatalysis performance.The simple SnO that uses
2and SnO is very limited in actual use as photochemical catalyst.
Improving tin oxygen compound photocatalysis performance main stream approach has: pattern and size are controlled to increase its efficiency of light absorption and light-catalyzed reaction area; Improve photocatalysis performance and realize photocatalysis under visible ray by introducing low-gap semiconductor formation hetero-junctions, according to heterogeneous band structure feature, wherein
type heterogeneous semiconductor is owing to can realizing to a great extent the preferred material that is effectively separated into heterogeneous photochemical catalyst of photo-generated carrier.Although above main stream approach has improved semi-conductive photocatalysis performance to a certain extent, but still exist such as complex steps, the problem such as products therefrom amount is little, cost is expensive, thereby also limited the application at industrial circle.
Sn
3o
4as the homologous series oxide of tin-based oxide because it belongs to low-gap semiconductor, and experimentally preparation preparation SnO/Sn up to the present
3o
4also there is not report.The present invention has successfully realized SnO/Sn by traditional one step hydro thermal method first experimentally
3o
4low cost preparation, and this SnO/Sn
3o
4iI type heterojunction structure is expected to realize good photocatalysis performance under visible ray.
Summary of the invention
The present invention seeks to prepare one and be beneficial to and reduce production costs, 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 being placed in reactor, is to react under the condition of 180 DEG C in the temperature of mixed solution;
3) after having reacted, mixed system is cooled to normal temperature, taking precipitate replaces eccentric cleaning with deionized water and absolute ethyl alcohol, get solids dry at 60 DEG C after, take out product.
The invention has the advantages that SnO and Sn in synthetic product
3o
4two kinds of heterojunction structure products are also deposited, and have formed hollow flower-shapedly, have larger specific area and hollow bobbles structure, have very high efficiency of light absorption, and photocatalysis performance is high, and properties of catalyst is stablized non-secondary pollution.The inventive method, one-step synthesis, synthesis temperature is low, and preparation technology is simple, prepares required raw material cheap, and synthetic quantity is large, has solved traditional photochemical catalyst two steps or multistep and has synthesized 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 of preparing bigger serface and good 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.
Brief description of the drawings
Fig. 1 is the prepared SnO/Sn with high photocatalysis performance of example of the present invention
3o
4the x-ray diffraction pattern of II type heterojunction structure.
Fig. 2 is the prepared SnO/Sn with high photocatalysis performance of example of the present invention
3o
4the stereoscan photograph figure of II type heterojunction structure.
Fig. 3 is the prepared SnO/Sn with high photocatalysis performance of example of the present invention
3o
4the transmission electron microscope of II type heterojunction structure and SEAD figure.
Fig. 4 is the SnO/Sn of the prepared photocatalysis performance of example of the present invention
3o
4the band structure of the UV-Vis absorption properties of II type heterogeneous structure material and the hetero-junctions calculating thus.
The SnO/Sn of what Fig. 5 example of the present invention was prepared have high photocatalysis performance
3o
4the photocatalysis performance figure of II type heterojunction structure.
Detailed description of the invention
One, prepare heterojunction structure photochemical catalyst:
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 absolute ethyl alcohol of 140ml deionized water and 60ml.Stir after 2 hours, mixed solution is placed in to 200ml reactor, hydro-thermal reaction 18 hours at 180 DEG C; Then reactor is taken out under cold water cooling 0.5 hour fast, afterwards gained sediment is replaced to eccentric cleaning with deionized water and absolute ethyl alcohol, and products therefrom is dried to 12 hours at 60 DEG C, finally take out product.
Two, checking:
As Fig. 1, Fig. 2, Fig. 3, shown in Fig. 4, adopts D8 ADVANCE type XRD (Cu radiation,, German Bruker-AXS company) to measure the crystal phase structure of prepared sample.Adopt the S4800 of Hitachi, Ltd (Japan)
type FESEM (FESEM, s-4800
, Hitachi) pattern of prepared sample is observed.Adopt the Tecnai F30 field transmission Electronic Speculum (HRTEM, Tecnai F30, FEI) of Dutch philips-FEI company that the crystal phase structure of sample is surveyed intuitively and characterized.Adopt UV-Vis absorption properties and the band structure of Cary 5000 type ultraviolet-visible-near-infrared absorption spectrum instrument (Varian company of the U.S.) to sample to analyze.The photocatalysis performance that adopts XPA-7 type photochemical reaction instrument (Xujiang Electromechanical Plant, Nanjing, China) and UV-3600 type spectrometer (Japanese Shimadzu company) to carry out the degraded of RhB dyestuff to gained sample is tested.
Result of the test shows:
Fig. 1: the SnO/Sn of the prepared photocatalysis performance of 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 directions to 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 has illustrated SnO and Sn in prepared sample
3o
4coexist.
Fig. 2: the SnO/Sn of the prepared photocatalysis performance of example of the present invention
3o
4scanning/transmission electron microscope photo figure of II type heterojunction structure.Can find out from scanning electron microscope (SEM) photograph, the inventive method successfully realizes the flower-like nanometer ball of evenly preparing in large area, and diameter is greatly about 5 about μ m, and it can also be seen that from transmission electron microscope illustration the flower-like nanometer ball of preparing 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 prepared photocatalysis performance of example of the present invention
3o
4the high power transmission electron microscope of II type heterogeneous structure material and SEAD figure.Can find out from transmission electron microscope and the SEAD of high power the SnO/Sn with high photocatalysis performance that example is prepared
3o
4iI type heterogeneous structure material is by SnO and Sn
3o
4form.Wherein 0.192nm is corresponding to SnO (102 crystal face), and 0.315nm is corresponding to Sn
3o
4(111) face.
Fig. 4: the SnO/Sn of the prepared photocatalysis performance of example of the present invention
3o
4the band structure of the UV-Vis absorption properties of II type heterogeneous structure material and the hetero-junctions calculating 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.In figure, it can also be seen that SnO and Sn
3o
4belong to low-gap semiconductor (SnO (Eg=2.47eV at RT) and Sn
3o
4(Eg=2.19eV at RT), this SnO/Sn
3o
4iI type heterojunction structure is expected to realize good photocatalysis performance under visible ray.
Fig. 5: the SnO/Sn of what example of the present invention was prepared have high photocatalysis performance
3o
4iI type heterojunction structure photocatalysis performance figure.As can be seen from Fig., the SnO/Sn of synthesized of the present invention
3o
4iI type heterogeneous structure material just can be reduced to the concentration of original dyestuff below 8% at about about 90 minutes.
Known 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 ray.
Therefore, can find out from above-mentioned experimental procedure, data and graphic analyses, the present invention is the synthetic 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 (4)
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;
2) mixed solution being placed in reactor, is to react under the condition of 180 DEG C in the temperature of mixed solution;
3) after having reacted, mixed system is cooled to normal temperature, taking precipitate replaces eccentric cleaning with deionized water and absolute ethyl alcohol, get solids dry at 60 DEG C after, take out product.
2. preparation method according to claim 1, the ethanol mass percent that it is characterized in that described ethanol water is 60%.
3. preparation method according to claim 1, is characterized in that described NaOH, urea and SnCl
22H
2the mass ratio that feeds intake of O is 1.2:1:565.
4. according to preparation method described in claim 1 or 2 or 3, the rate of charge that it is characterized in that ethanol in described NaOH and ethanol water is 4g:75ml.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105036068A (en) * | 2015-06-17 | 2015-11-11 | 山东大学 | Composite material suitable for low-temperature ethanol sensor and application of composite material |
| 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 |
| CN106000384A (en) * | 2016-05-13 | 2016-10-12 | 淮北师范大学 | Preparation method of tin-based oxide with controllable components and photocatalytic application of tin-based oxide |
| 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 |
| 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 |
| WO2019107152A1 (en) * | 2017-12-01 | 2019-06-06 | 三菱マテリアル株式会社 | Method for producing photocatalyst |
| CN110064386A (en) * | 2019-05-30 | 2019-07-30 | 济南大学 | A kind of three tin nanometer sheet composite photocatalyst materials of oxidation of tool Lacking oxygen four and preparation method of tin nanoparticles modification |
| CN110668416A (en) * | 2019-10-08 | 2020-01-10 | 扬州大学 | Photocatalytic reduction of CO2Method (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 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| 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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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105036068A (en) * | 2015-06-17 | 2015-11-11 | 山东大学 | Composite material suitable for low-temperature ethanol sensor and application of composite material |
| CN106000384A (en) * | 2016-05-13 | 2016-10-12 | 淮北师范大学 | Preparation method of tin-based oxide with controllable components and photocatalytic application of tin-based oxide |
| 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 |
| JP2019098245A (en) * | 2017-12-01 | 2019-06-24 | 三菱マテリアル株式会社 | Manufacturing method of photocatalyst |
| WO2019107152A1 (en) * | 2017-12-01 | 2019-06-06 | 三菱マテリアル株式会社 | Method for producing photocatalyst |
| 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 |
| CN110064386A (en) * | 2019-05-30 | 2019-07-30 | 济南大学 | A kind of three tin nanometer sheet composite photocatalyst materials of oxidation of tool Lacking oxygen four and preparation method of tin nanoparticles modification |
| 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 |
| CN110668416A (en) * | 2019-10-08 | 2020-01-10 | 扬州大学 | Photocatalytic reduction of CO2Method (2) |
| 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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