CN107265495A - Non-template method prepares zinc sulphide microballoon - Google Patents
Non-template method prepares zinc sulphide microballoon Download PDFInfo
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- CN107265495A CN107265495A CN201710595749.9A CN201710595749A CN107265495A CN 107265495 A CN107265495 A CN 107265495A CN 201710595749 A CN201710595749 A CN 201710595749A CN 107265495 A CN107265495 A CN 107265495A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/08—Sulfides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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Abstract
The invention provides one kind different crystal forms are prepared using hydro-thermal method（Zincblende and buergerite）The method of zinc sulphide microballoon.By controlling thiourea concentration, sintering temperature, the transformation between the generation control of zinc sulphide microballoon and different crystal forms is realized.Realized particular by following steps, with sulfur-containing compounds such as thiocarbamides（Hydrolysis can produce the compound of sulphion）For sulphur source, using zinc compounds such as two water zinc acetates as zinc source, it is added in deionized water, then hydro-thermal 24 hours at a certain temperature.After reaction terminates, washing, 80 °C of dryings 6 hours.Obtained sample is calcined at a certain temperature, obtains the zinc sulphide microballoon of different-shape and crystal formation.Preparation technology of the present invention is simple, and obtained zinc sulphide has different patterns and crystal formation, and catalyst can reclaim reuse, is had a wide range of applications in fields such as photocatalysis.The optimum condition of obtained zinc sulphide microballoon is：Zn2+:Thiocarbamide mol ratio is 1:2, during 400 °C of sintering temperature, the photocatalysis effect of correspondence product is best.
Description
Technical field
The method that the zinc sulphide microballoon of different-shape and crystal formation is prepared the present invention relates to non-template method, belongs to photocatalysis technology
Field.
Background technology
Zinc sulphide is a kind of one of important II-IV races semi-conducting material, superior performance, in LED, solar cell, light
The fields such as catalysis have all shown huge potentiality, are expected to replace traditional II-IV races halfbody base prepared by complex technology
Matter.Zinc sulphide is nontoxic, uses safety.Zinc sulphide has two kinds of crystal structures, and respectively band-gap energy is 3.72ev cube
Zincblende lattce structure and the hexagonal wurtzite structure that band-gap energy is 3.77ev.Wurtzite structure is high-temperature-phase（α-zinc sulphide）, dodge
Zinc ore structure is low-temperature phase（β-zinc sulphide）, buergerite is mutually that thermodynamics is metastable, and it forms temperature than zincblende phase
It is high.It is worth noting that, the optical property of buergerite zinc sulphide is better than zincblende phase.Therefore, it is necessary to carefully control synthesis condition
To obtain buergerite zinc sulphide, suppress transformation of the buergerite zinc sulphide to zincblende zinc sulphide.Prepare zinc sulphide microballoon at present
Method mainly has：Hydro-thermal method, chemical vapour deposition technique, template etc..Hydro-thermal method is using water as solvent, in high temperature and high pressure environment
The method of reaction generation superfines precipitation.Hydro-thermal method preparation technology is simple, cost is low, can prepare size, morphology controllable
Zinc sulphide microballoon, good dispersion, crystallinity is high.
Zinc source is dissolved in the solvent of the mixture formation of water or alcohols or ketone by patent CN 106745197-A, is added
Sulphur source, sealing reaction at least 24 hours under 95-150 °C, reactant is cooled to room temperature, separates, washs, is dried to obtain sulphur
Change zinc microballoon.Zinc sulphide microballoon formed in it has core-shell structure, and its shell core is constituted by zinc sulphide crystal grain.It uses mould
Plate method prepares the smooth zinc sulphide microballoon in surface, complex operation.
The content of the invention
Purpose of the present invention control synthesis condition prepares morphology controllable and reusable microballoon zinc sulphide.This preparation
Procedure is simple, and reaction condition is gentle, raw materials used green pollution-free.And because the microballoon zinc sulphide has difference
Pattern, in terms of photocatalysis have potential application.It is characterized in that methods described is comprised the steps of：
(1) a certain amount of thiocarbamide is weighed with assay balance, 60ml distilled water is measured with graduated cylinder, polytetrafluoroethylene (PTFE) material is added to
Reactor inner bag, is stirred on magnetic stirring apparatus to solution clarification；
(2) a certain amount of two water zinc acetate is weighed with assay balance, is added in above-mentioned solution, stirred on magnetic stirring apparatus to
Solution is clarified；
(3) reactor is put into baking oven, reacted 24 hours；
(4) reaction naturally cools to room temperature after terminating；
(5) inorganic filter membrane is selected, suction filtration is carried out with vavuum pump, during suction filtration, is constantly rinsed with distilled water；
(6) solid sample is put into evaporating dish together with filter membrane, be then placed in baking oven, 80 °C of dryings 6 hours；
(7) dried sample is clayed into power with mortar, sample is then put into porcelain boat, be then placed in argon gas in tube furnace and protect
Shield is lower to be heated, and 10 °C/min of heating and cooling is heated 0.5 hour；
So far the present invention is on two kinds of crystalline phases, and prepared by the microballoon zinc sulphide of morphology controllable finishes.
The advantage of invention is：
(1) solvent used is deionized water in preparing, and raw material is zinc acetate dihydrate, thiocarbamide, and not only production cost is low, green
It is environment friendly and pollution-free, and products obtained therefrom crystallinity is higher；
(2) preparation technology is simply controllable, reproducible, and the regulation and control of pattern and crystalline phase for microballoon zinc sulphide need to only control sulphur
Urea concentration, sintering temperature, it is workable；
(3) sample prepared by is conducive to reclaiming and may be reused, with very long service life.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph for preparing zinc sulphide microballoon；
Fig. 2 is the X-ray diffractogram of example 1-3 zinc sulphide microballoons；
Fig. 3 is example 2, the X-ray diffractogram of 4-5 zinc sulphide microballoons；
Fig. 4 is the photocatalysis figure of example 1-3 zinc sulphide microballoons；
Fig. 5 is example 2, the photocatalysis figure of 4-5 zinc sulphide microballoons.
Embodiment
Below with specific embodiment come the present invention will be further described, it should be appreciated that, following inventions merely to
The present invention is explained, its content is not defined.
Example 1
(1) 0.4613 gram of thiocarbamide is weighed with assay balance, 60ml distilled water is measured, the reaction of polytetrafluoroethylene (PTFE) material is added to
Kettle inner bag, is stirred on magnetic stirring apparatus to solution clarification；
(2) 1.3304 grams of zinc acetate dihydrates are weighed with assay balance, are added in above-mentioned solution, are stirred on magnetic stirring apparatus
To solution clarification；
(3) reactor is put into baking oven, 180 °C are reacted 24 hours；
(4) reaction naturally cools to room temperature after terminating；
(5) inorganic filter membrane is selected, suction filtration is carried out with vavuum pump, during suction filtration, is constantly rinsed with distilled water；
(6) solid sample is put into evaporating dish together with filter membrane, be then placed in baking oven, 80 °C of dryings 6 hours；
(7) dried sample is clayed into power with mortar, sample is then put into porcelain boat, be then placed in argon gas in tube furnace and protect
Shield is lower to be heated, 10 °C/min of heating and cooling, and 400 °C are heated 0.5 hour.
Example 2
(1) 0.9227 gram of thiocarbamide is weighed with assay balance, 60ml distilled water is measured, the reactor of polytetrafluoroethylene (PTFE) material is added to
Inner bag, is stirred on magnetic stirring apparatus to solution clarification；
(2) 1.3304 grams of zinc acetate dihydrates are weighed with assay balance, are added in above-mentioned solution, are stirred on magnetic stirring apparatus
To solution clarification；
(3) reactor is put into baking oven, 180 °C are reacted 24 hours；
(4) reaction naturally cools to room temperature after terminating；
(5) inorganic filter membrane is selected, suction filtration is carried out with vavuum pump, during suction filtration, is constantly rinsed with distilled water；
(6) solid sample is put into evaporating dish together with filter membrane, be then placed in baking oven, 80 °C of dryings 6 hours；
(7) dried sample is clayed into power with mortar, sample is then put into porcelain boat, be then placed in argon gas in tube furnace and protect
Shield is lower to be heated, 10 °C/min of heating and cooling, and 400 °C are heated 0.5 hour.
Example 3
(1) 1.8453 grams of thiocarbamides are weighed with assay balance, 60ml distilled water is measured, the reaction of polytetrafluoroethylene (PTFE) material is added to
Kettle inner bag, is stirred on magnetic stirring apparatus to solution clarification；
(2) 1.3304 grams of zinc acetate dihydrates are weighed with assay balance, are added in above-mentioned solution, are stirred on magnetic stirring apparatus
To solution clarification；
(3) reactor is put into baking oven, 180 °C are reacted 24 hours；
(4) reaction naturally cools to room temperature after terminating；
(5) inorganic filter membrane is selected, suction filtration is carried out with vavuum pump, during suction filtration, is constantly rinsed with distilled water；
(6) solid sample is put into evaporating dish together with filter membrane, be then placed in baking oven, 80 °C of dryings 6 hours；
(7) dried sample is clayed into power with mortar, sample is then put into porcelain boat, be then placed in argon gas in tube furnace and protect
Shield is lower to be heated, 10 °C/min of heating and cooling, and 400 °C are heated 0.5 hour.
Example 4
(1) 0.9227 gram of thiocarbamide is weighed with assay balance, 60ml distilled water is measured, the reactor of polytetrafluoroethylene (PTFE) material is added to
Inner bag, is stirred on magnetic stirring apparatus to solution clarification；
(2) 1.3304 grams of zinc acetate dihydrates are weighed with assay balance, are added in above-mentioned solution, are stirred on magnetic stirring apparatus
To solution clarification；
(3) reactor is put into baking oven, 180 °C are reacted 24 hours；
(4) reaction naturally cools to room temperature after terminating；
(5) inorganic filter membrane is selected, suction filtration is carried out with vavuum pump, during suction filtration, is constantly rinsed with distilled water；
(6) solid sample is put into evaporating dish together with filter membrane, be then placed in baking oven, 80 °C of dryings 6 hours；
(7) dried sample is clayed into power with mortar, sample is then put into porcelain boat, be then placed in argon gas in tube furnace and protect
Shield is lower to be heated, 10 °C/min of heating and cooling, and 500 °C are heated 0.5 hour.
Example 5
(1) 0.9227 gram of thiocarbamide is weighed with assay balance, 60ml distilled water is measured, the reactor of polytetrafluoroethylene (PTFE) material is added to
Inner bag, is stirred on magnetic stirring apparatus to solution clarification；
(2) 1.3304 grams of zinc acetate dihydrates are weighed with assay balance, are added in above-mentioned solution, are stirred on magnetic stirring apparatus
To solution clarification；
(3) reactor is put into baking oven, 180 °C are reacted 24 hours；
(4) reaction naturally cools to room temperature after terminating；
(5) inorganic filter membrane is selected, suction filtration is carried out with vavuum pump, during suction filtration, is constantly rinsed with distilled water；
(6) solid sample is put into evaporating dish together with filter membrane, be then placed in baking oven, 80 °C of dryings 6 hours；
(7) dried sample is clayed into power with mortar, sample is then put into porcelain boat, be then placed in argon gas in tube furnace and protect
Shield is lower to be heated, 10 °C/min of heating and cooling, and 600 °C are heated 0.5 hour.
Claims (7)
1. a kind of microballoon zinc sulphide, its preparation is characterised by：Zinc sulphide is controlled by changing the conditions such as thiourea concentration, sintering temperature
Pattern and crystal formation, prepare zinc sulfide nano microballoon with simple one step hydro thermal method.
2. the preparation method of zinc sulphide microballoon as claimed in claim 1, it is characterised in that the described method comprises the following steps：
(a) sulphur source is dissolved in deionized water, zinc source is added under stirring condition, the solution stirred to clarify is exactly that presoma is molten
Liquid；
(b) reactor that will be equipped with precursor solution is put into baking oven heating；
(c) reacted solid is washed with deionized three times, is dried to obtain precursor powder；
(d) microballoon zinc sulphide is made in tubular type kiln roasting in precursor powder after cooling.
3. the preparation method of zinc sulphide microballoon as claimed in claim 2, it is characterised in that in the step (a), sulphur source is
Sulfur-containing compound, such as soluble sulfosalt and hydrolysis can produce the compound of sulphion, such as vulcanized sodium, thiocarbamide, sulfydryl third
Propylhomoserin, the present invention preferably thiocarbamide；Zinc source is zinc compound, for example zinc sulfate, zinc nitrate, zinc chloride, zinc acetate etc., the present invention
It is preferred that zinc acetate.
4. the preparation method of zinc sulphide microballoon as claimed in claim 3, Zn2+Concentration is 0.05-0.5 mol/L, Zn2+：Sulphur
Urea mol ratio is 1:1-4, the present invention preferably Zn2+Concentration 0.1 mol/L, Zn2+：Thiocarbamide mol ratio is 1:2.
5. the preparation method of zinc sulphide microballoon as claimed in claim 2, it is characterised in that in the step (b), synthesis temperature
Spend for 80-220 °C, 12-48 hours reaction time, preferably 180 °C of the present invention reacts 24 hours.
6. the preparation method of zinc sulphide microballoon as claimed in claim 2, it is characterised in that in the step (c), solid-like
The drying temperature of product is 60-80 °C, and drying time is 6-24 hours.
7. the preparation method of zinc sulphide microballoon as claimed in claim 2, it is characterised in that in the step (d), heating speed
Degree is that 5-10 °C/min sintering temperatures are 400 °C-600 °C, the present invention preferably 10 °C/min, 400 °C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710595749.9A CN107265495A (en) | 2017-07-20 | 2017-07-20 | Non-template method prepares zinc sulphide microballoon |
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| CN201710595749.9A CN107265495A (en) | 2017-07-20 | 2017-07-20 | Non-template method prepares zinc sulphide microballoon |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109292813A (en) * | 2018-10-18 | 2019-02-01 | 温州大学新材料与产业技术研究院 | A kind of method that hydrothermal synthesis method prepares ZnS microballoon |
| CN109638244A (en) * | 2018-12-05 | 2019-04-16 | 岭南师范学院 | A kind of zinc sulphide@carbon complex microsphere and the preparation method and application thereof |
| CN109987624A (en) * | 2019-05-10 | 2019-07-09 | 长沙学院 | The preparation method of ZnS nanosheet |
| CN110304650A (en) * | 2019-06-17 | 2019-10-08 | 哈尔滨理工大学 | A kind of preparation and application of zinc sulfide nano ball array/foamy graphite alkene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102614897A (en) * | 2012-03-12 | 2012-08-01 | 中国科学院福建物质结构研究所 | Annealing treatment method for improving photo-catalytic activity of zinc sulfide material |
| CN106238071A (en) * | 2016-07-11 | 2016-12-21 | 陕西科技大学 | A kind of method using absorption calcination method to prepare ZnS@C composite |
| CN106517308A (en) * | 2015-09-15 | 2017-03-22 | 宿迁学院 | Preparation method of ZnS hollow microspheres |
-
2017
- 2017-07-20 CN CN201710595749.9A patent/CN107265495A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102614897A (en) * | 2012-03-12 | 2012-08-01 | 中国科学院福建物质结构研究所 | Annealing treatment method for improving photo-catalytic activity of zinc sulfide material |
| CN106517308A (en) * | 2015-09-15 | 2017-03-22 | 宿迁学院 | Preparation method of ZnS hollow microspheres |
| CN106238071A (en) * | 2016-07-11 | 2016-12-21 | 陕西科技大学 | A kind of method using absorption calcination method to prepare ZnS@C composite |
Non-Patent Citations (1)
| Title |
|---|
| JINGANG ZHAO ET AL.: ""Surfactant-free hydrothermal synthesis and optical properties of ZnS solid microspheres"", 《MATERIALS LETTERS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109292813A (en) * | 2018-10-18 | 2019-02-01 | 温州大学新材料与产业技术研究院 | A kind of method that hydrothermal synthesis method prepares ZnS microballoon |
| CN109638244A (en) * | 2018-12-05 | 2019-04-16 | 岭南师范学院 | A kind of zinc sulphide@carbon complex microsphere and the preparation method and application thereof |
| CN109987624A (en) * | 2019-05-10 | 2019-07-09 | 长沙学院 | The preparation method of ZnS nanosheet |
| CN110304650A (en) * | 2019-06-17 | 2019-10-08 | 哈尔滨理工大学 | A kind of preparation and application of zinc sulfide nano ball array/foamy graphite alkene |
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