CN106517308A - Preparation method of ZnS hollow microspheres - Google Patents
Preparation method of ZnS hollow microspheres Download PDFInfo
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- CN106517308A CN106517308A CN201510585000.7A CN201510585000A CN106517308A CN 106517308 A CN106517308 A CN 106517308A CN 201510585000 A CN201510585000 A CN 201510585000A CN 106517308 A CN106517308 A CN 106517308A
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Abstract
The invention discloses a preparation method of ZnS hollow microspheres. The method comprises the following steps: (1) NaOH powder, thiourea powder and zinc acetate which are prepared in parts by weight are dissolved in an absolute ethyl alcohol solution which is prepared by deionized water and absolute ethyl alcohol, and a mixed solution is prepared; (2) the mixed solution prepared in the step (1) is stirred for 1.5-2.5 hours and placed in a reaction vessel, and a hydrothermal reaction is carried out at 170-190 DEG C for 15-17 hours; (3) after the reaction ends, the reaction vessel is taken out and naturally cooled at a room temperature, obtained precipitate is centrifuged and cleaned alternatively with deionized water and absolute ethyl alcohol, and cleaned solid products are dried at 55-65 DEG C for 11-13 hours. The preparation technology is simple with one-step synthesis, synthesis temperature is low, and the yield is high; the sample has the advantages of larger specific surface area and hollow structure, high luminous absorption efficiency, and stable photocatalyst performance without secondary pollution; and the problems of two-step or multi-step synthesis of traditional photocatalysts and high preparation cost are solved.
Description
Technical field
The present invention relates to photocatalysis technology field, and in particular to a kind of a kind of preparation method of ZnS hollow sub-microsphere of the synthesis first with high-performance optical catalytic capability.
Background technology
Traditional method of wastewater treatment（Such as filtration, thin film separation, sedimentation and absorption etc.）Typically organic dye pollutant is transferred in solid phase from liquid phase, these organic things that stain are not resolved into into harmless material fundamentally, therefore, the improvement of waste water from dyestuff is that Now Domestic external environment science is badly in need of a great problem to be solved.It is a kind of new method that Recent study is developed using Photocatalitic Technique of Semiconductor environment purification, semiconductor light-catalyst has very strong catalysis activity, under the irradiation of sunlight or ultraviolet source, harmful substance in organic wastewater can be changed into the innocuous substances such as CO2, water, so as to reach the purpose for administering waste water, therefore, waste water from dyestuff is administered by light-catalyzed reaction and there is boundless application prospect.
ZnS materials（Eg=3.68eV at RT）Be a kind of semiconductor material with wide forbidden band with significant application value, with excellent fluorescent effect and electroluminescent function, many excellent performances are presented in fields such as electricity, magnetics, optics, mechanics and catalysis.Due to these excellent properties and being widely applied, people explore the methods and techniques of many to synthesize this important material.Such as vapour deposition process, template etc., but these methods often have scale topography and be difficult to control, yield is not high, and pyroreaction condition is harsh, fabricating technology is complicated, high cost the shortcomings of.
Tiny balloon is also referred to as hollow ball shell material, and its particle diameter, from nanoscale to micron order, is that core-shell particles remove core by means such as heat treatment, dissolvings or control certain reaction condition, a kind of new structure obtained under specific physics chemical action.Hollow microsphere material is because of increased attention in recent years the advantages of its relatively low density, larger specific surface area, preferable Surface Permeability and structural stability.Although the technology of synthesis tiny balloon is gone to design and prepare a kind of semi-conducting material with excellent optical performance using simple one-step method for synthesizing, still suffers from huge challenge achieved with sizable progress at present.
The content of the invention
The present invention can make material list reveal the performance not available for general common material based on the pattern and size for changing material, so as to improve the photocatalysis performance of material, there is provided a kind of preparation method of the ZnS hollow sub-microspheres that preparation cost is low, efficiency of light absorption is high, properties of catalyst is stable.
Technical solution of the present invention：
A kind of preparation method of ZnS hollow sub-microspheres, it is characterised in that：Including following preparation process：
（1）The NaOH powder of proportion by weight, thiourea powder, zinc acetate are dissolved in the ethanol solution by obtained in deionized water and dehydrated alcohol, mixed solution is obtained；
（2）By step（1）In obtained mixed solution stir 1.5～2.5 hours after be placed in reactor, hydro-thermal reaction 15～17 hours at a temperature of 170～190 DEG C；
（3）After reaction terminates, reactor is taken out into natural cooling at room temperature, gained sediment deionized water and dehydrated alcohol alternating centrifugal are cleaned, and the solid product after cleaning is dried 11～13 hours at 55～65 DEG C, the final product ZnS that the present invention is obtained.
The step（1）Middle deionized water（Volume）：Dehydrated alcohol（Volume）=1：1, in obtained mixed solution, NaOH concentration is 5mol/L, and thiourea concentration is 0.075mol/L, and zinc acetate concentration is 0.05mol/L.
The step（1）The purity of middle NaOH powder is 99.99%, and thiourea powder, the purity of zinc acetate are 99.999%.
The step（2）The specification of middle reactor is 200ml～1 × 106ml。
Preferably, the step（2）Middle mixing time is 2 hours.
Preferably, the step（2）Middle hydrothermal temperature is 180 DEG C, and the hydro-thermal reaction time is 16 hours.
Preferably, the step（3）The baking temperature of the solid product after middle cleaning is 60 DEG C, and drying time is 12 hours.
Beneficial effects of the present invention：The present invention has synthesized the ZnS hollow sub-microspheres with high photocatalysis performance first, raw material is cheap, preparation process is simple, one-step synthesis, synthesis temperature are low, prepare products therefrom amount big, obtained sample has larger specific surface area and hollow-core construction, efficiency of light absorption is high, the stable non-secondary pollution of properties of catalyst, solves the problems, such as two step of traditional photocatalyst or multistep synthesis and preparation cost is high.
Description of the drawings
Fig. 1 is the x-ray diffraction pattern of the ZnS with high photocatalysis performance prepared by the embodiment of the present invention.
Fig. 2 is the stereoscan photograph figure of the ZnS with high photocatalysis performance prepared by the embodiment of the present invention.
Fig. 3 is the stereoscan photograph figure of the ZnS with high photocatalysis performance prepared by the embodiment of the present invention.
Fig. 4 is the transmission electron microscope photo figure of the ZnS with high photocatalysis performance prepared by the embodiment of the present invention.
Fig. 5 is the photocatalysis performance figure of the ZnS with high photocatalysis performance prepared by the embodiment of the present invention.
Specific embodiment
With reference to specific embodiment, the present invention will be further described.
Embodiment 1
Choose NaOH powder（32g）, thiourea powder（0.913g）, zinc acetate（1.756g）In the mixed solution of the dehydrated alcohol for being dissolved in 80ml deionized waters and 80ml；After stirring 2 hours, mixed solution is placed in into 200ml reactors, hydro-thermal reaction 16 hours at 180 DEG C；Then reactor is taken out into the natural cooling under room temperature, afterwards gained sediment deionized water and dehydrated alcohol alternating centrifugal is cleaned, and products therefrom is dried 12 hours at 60 DEG C, the final product ZnS 0.61g that the present invention is obtained.
Embodiment 2
Choose NaOH powder（16g）, thiourea powder（0.457g）, zinc acetate（0.878g）In the mixed solution of the dehydrated alcohol for being dissolved in 40ml deionized waters and 40ml；After stirring 2 hours, mixed solution is placed in into 100ml reactors, hydro-thermal reaction 15 hours at 170 DEG C；Then reactor is taken out into the natural cooling under room temperature, afterwards gained sediment deionized water and dehydrated alcohol alternating centrifugal is cleaned, and products therefrom is dried 12 hours at 60 DEG C, the final product ZnS 0.31g that the present invention is obtained.
Embodiment 3
Choose NaOH powder（20g）, thiourea powder（0.571g）, zinc acetate（1.098g）In the mixed solution of the dehydrated alcohol for being dissolved in 50ml deionized waters and 50ml；After stirring 1.5 hours, mixed solution is placed in into 120ml reactors, hydro-thermal reaction 17 hours at 190 DEG C；Then reactor is taken out into the natural cooling under room temperature, afterwards gained sediment deionized water and dehydrated alcohol alternating centrifugal is cleaned, and products therefrom is dried 12 hours at 60 DEG C, the final product ZnS 0.36g that the present invention is obtained.
Performance evaluation test is carried out to final product obtained in above-described embodiment：As shown in figure 1, adopting D8 ADVANCE types XRD（Cu radiation, German Bruker-AXS companies）The crystal phase structure of sample prepared by determining；As shown in Figure 2 and Figure 3, using Hitachi, Ltd（Japan）II types FESEM of S4800 (FESEM, s-4800 II, Hitachi) pattern of prepared sample is observed；As shown in figure 4, Tecnai F30 Flied emission transmission electron microscopes (HRTEM, Tecnai F30, FEI) using philips-FEI companies of Holland is intuitively detected and is characterized to the crystal phase structure of sample；As shown in figure 5, adopting XPA-7 type photochemical reaction instrument（Xujiang Electromechanical Plant, Nanjing, China）With UV-3600 type spectrogrphs（Japanese Shimadzu Corporation）The photocatalysis performance test of RhB dyestuff degradeds is carried out to gained sample.
Fig. 1：The x-ray diffraction pattern of the ZnS with high photocatalysis performance prepared by the embodiment of the present invention.All of diffraction maximum shown in master map from left to right corresponds respectively to cubic zinc blende ZnS（111）,（200）,（220）,（311）,（400）,（420）, it is illustrated that XRD illustrates that the sample prepared by the present invention is ZnS materials.
Fig. 2：The stereoscan photograph figure of the ZnS with high photocatalysis performance prepared by the embodiment of the present invention.Knowable to the figure, the ZnS with high photocatalysis performance prepared by embodiment is the micron ball with large specific surface area, and diameter is at 4 μm or so.
Fig. 3：The stereoscan photograph figure of the ZnS with high photocatalysis performance prepared by the embodiment of the present invention.Knowable to the figure, the ZnS with high photocatalysis performance prepared by embodiment is the hollow-core construction with large specific surface area, and this pattern is more beneficial for the raising of photocatalysis performance.
Fig. 4：The high power transmission electron microscope photo figure of the ZnS with high photocatalysis performance prepared by the embodiment of the present invention.Can be seen that from the transmission electron microscope of high power the material with high photocatalysis performance prepared by embodiment is made up of ZnS, wherein 1.91 corresponding to ZnS's（220）Face, 2.71 corresponding to ZnS's（200）Face.
Fig. 5：The ZnS photocatalysis performance figures with high photocatalysis performance prepared by the embodiment of the present invention.As can be seen from Fig., the concentration of original dyestuff just can be reduced to less than 8% at 100 minutes or so by the ZnS materials synthesized by the present invention.
ZnS materials preparation procedure with high photocatalysis performance prepared by the present invention is simple, with low cost, and synthetic quantity is big, and has preferable photo-catalysis capability, therefore can promote and be applied to industrial circle.
Therefore, present invention ZnS material of the synthesis with high photocatalysis performance first is can be seen that from above-mentioned experimental procedure, data and graphic analyses, and preparation process is simple, it is with low cost, it is suitable to commercial Application.
Claims (7)
1. a kind of preparation method of ZnS hollow sub-microspheres, it is characterised in that：Including following preparation process：
（1）The NaOH powder of proportion by weight, thiourea powder, zinc acetate are dissolved in the ethanol solution by obtained in deionized water and dehydrated alcohol, mixed solution is obtained；
（2）By step（1）In obtained mixed solution stir 1.5～2.5 hours after be placed in reactor, hydro-thermal reaction 15～17 hours at a temperature of 170～190 DEG C；
（3）After reaction terminates, reactor is taken out into natural cooling at room temperature, gained sediment deionized water and dehydrated alcohol alternating centrifugal are cleaned, and the solid product after cleaning is dried 11～13 hours at 55～65 DEG C, the final product ZnS that the present invention is obtained.
2. as claimed in claim 1 a kind of preparation method of ZnS hollow sub-microspheres, it is characterised in that：The step（1）Middle deionized water（Volume）：Dehydrated alcohol（Volume）=1：1, in obtained mixed solution, NaOH concentration is 5mol/L, and thiourea concentration is 0.075mol/L, and zinc acetate concentration is 0.05mol/L.
3. as claimed in claim 1 a kind of preparation method of ZnS hollow sub-microspheres, it is characterised in that：The step（1）The purity of middle NaOH powder is 99.99%, and thiourea powder, the purity of zinc acetate are 99.999%.
4. step described in（2）The specification of middle reactor is 200ml～1 × 106ml。
5. as claimed in claim 1 a kind of preparation method of ZnS hollow sub-microspheres, it is characterised in that：The step（2）Middle mixing time is 2 hours.
6. as claimed in claim 1 a kind of preparation method of ZnS hollow sub-microspheres, it is characterised in that：The step（2）Middle hydrothermal temperature is 180 DEG C, and the hydro-thermal reaction time is 16 hours.
7. as claimed in claim 1 a kind of preparation method of ZnS hollow sub-microspheres, it is characterised in that：The step（3）The baking temperature of the solid product after middle cleaning is 60 DEG C, and drying time is 12 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107265495A (en) * | 2017-07-20 | 2017-10-20 | 济南大学 | Non-template method prepares zinc sulphide microballoon |
| CN114988458A (en) * | 2022-06-15 | 2022-09-02 | 江西八六三实业有限公司 | Method for preparing ZnS crystal based on control of morphology of copper-based catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101486487A (en) * | 2008-01-16 | 2009-07-22 | 中国科学院合肥物质科学研究院 | Zinc sulfide micron hollow sphere and preparation method thereof |
| CN102249289A (en) * | 2011-05-27 | 2011-11-23 | 新疆大学 | Method for preparing spiauterite ZnS fine nanorod with solvothermal method |
| CN104876256A (en) * | 2015-04-20 | 2015-09-02 | 河南师范大学 | Preparation method of water-soluble zinc sulfate quantum dot |
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2015
- 2015-09-15 CN CN201510585000.7A patent/CN106517308A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101486487A (en) * | 2008-01-16 | 2009-07-22 | 中国科学院合肥物质科学研究院 | Zinc sulfide micron hollow sphere and preparation method thereof |
| CN102249289A (en) * | 2011-05-27 | 2011-11-23 | 新疆大学 | Method for preparing spiauterite ZnS fine nanorod with solvothermal method |
| CN104876256A (en) * | 2015-04-20 | 2015-09-02 | 河南师范大学 | Preparation method of water-soluble zinc sulfate quantum dot |
Non-Patent Citations (1)
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| YIDONG ZHANG等: "Self-template hydrothermal synthesis ZnS microspheres", 《CRYST. RES. TECHNOL.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107265495A (en) * | 2017-07-20 | 2017-10-20 | 济南大学 | Non-template method prepares zinc sulphide microballoon |
| CN114988458A (en) * | 2022-06-15 | 2022-09-02 | 江西八六三实业有限公司 | Method for preparing ZnS crystal based on control of morphology of copper-based catalyst |
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Application publication date: 20170322 |