CN105819496B - A kind of preparation method of hollow silver sulfide nanometer particles microballoon - Google Patents
A kind of preparation method of hollow silver sulfide nanometer particles microballoon Download PDFInfo
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- CN105819496B CN105819496B CN201610159431.1A CN201610159431A CN105819496B CN 105819496 B CN105819496 B CN 105819496B CN 201610159431 A CN201610159431 A CN 201610159431A CN 105819496 B CN105819496 B CN 105819496B
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- microballoon
- silver sulfide
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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
- 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
- C01P2004/34—Spheres hollow
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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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- 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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Abstract
The invention discloses a kind of preparation method of hollow silver sulfide nanometer particles microballoon, using liquid-phase precipitation method, silver-colored source is provided with the hydrolysis of inorganic silver nitrate, sulphur source is hydrolyzed in acid condition with organic sodium thiosulfate to participate in and the hollow silver sulfide nanometer particles microballoon of silver ion reaction generation, any activating agent and stabilizer are added without in reaction, reaction at room temperature can obtain hollow silver sulfide nanometer particles microballoon.The inventive method is simple, and reaction is gentle, consumes energy small, synthesis step is few, simple to operate, to equipment without particular/special requirement, is adapted to large-scale production.It is demonstrated experimentally that obtained is hollow silver sulfide nanometer particles microballoon, a diameter of 1 3um of hollow silver sulfide nanometer particles microballoon.
Description
Technical field
The present invention is attributable to inorganic functional material preparing technical field, and it particularly relates to a kind of hollow silver sulfide nanometer particles
The preparation method of microballoon.
Background technology
In recent years, the various nano materials with special construction and special appearance cause extensive concern, one of them
It is hollow microsphere type nano structural material.Hollow microsphere be by core/shell composite structure material is developed, can be different by adjusting
The structure and size and composition of matter core shell compound particle reach the controllable adjustment to its property, thus realize to its optics, calorifics,
The a wide range of cutting of electricity, magnetics and catalytic property.What they were generally made up of nano particle, its size is in nanometer to micron
Scope, the multiple dimensioned multi-level nano material with hollow structure.Because the material of this class formation has low-density, high-ratio surface
Characteristic, and its hollow parts can accommodate substantial amounts of guest molecule or large-sized object, can produce some peculiar bases
In the property of microcosmic " parcel " effect so that hollow microsphere material nanometer waveguide, efficiently sensing, optical transport, catalytic separation,
The various fields such as medical diagnosis, targeted therapy, thermal acoustic insulation have broad application prospects.
Silver sulfide is a kind of important Transition-metal dichalcogenide, even more a kind of important typical n-type semiconductor material
Material, while silver sulfide is also the semi-conducting material of narrow band gap.Hollow silver sulfide nanometer particles microballoon is special due to its unique physical chemistry
Property, such as low-density, high-specific surface area, comprising inner space and the features such as surface penetration, and in opto-electronic conversion, photocatalysis, storage
The special nature shown in terms of hydrogen performance, electrode material, biological medicine.Therefore nanostructured silver sulfide photocatalysis,
The fields such as photoelectric conversion, solar cell, solar energy irradiation receiver, lithium-hydrogen battery, optical-electrical converter and biological medicine have
It is widely applied prospect.And then micro-nano silver sulfide turns into numerous disciplinary study person concerns such as material, physics, chemistry, photoelectricity
With the focus of research.At present, new material is made by simple and feasible synthetic method and corresponding experiment can be changed
Condition controls the pattern of synthetic, particularly synthesizes nanometer spherical, square and vermiform nano material and more causes largely
The interest of material physical and chemical performance researcher.There are many experimental methods to be used in nanoscale silver sulfide semiconductor material now
In the preparation of material, such as：Chemical deposition, hydro-thermal method, electrodeposition process, solvent-thermal method, template contral method in situ, microwave assisting method
Deng.
Synthesize nanoparticle just increasingly complex, it is common prepare nano-scale particle be need under conditions of HTHP or
Person adds surfactant（CTAB）It can just obtain.
The content of the invention
In view of prior art is not enough above, it is an object of the present invention to provide a kind of preparation side of hollow silver sulfide nanometer particles microballoon
Method, this method equipment is simple, and energy consumption is low, and synthesis step is few, simple to operate, at room temperature（25 DEG C or so）It can react, be adapted to big
Large-scale production, and the function admirable of silver sulfide is made, purity is high.
The present invention realizes that the technical scheme that the mesh of its invention is used is：A kind of preparation side of hollow silver sulfide nanometer particles microballoon
Method, its specific practice is：
A, preparation mixed solution
The sodium thiosulfate solution of certain density silver nitrate aqueous solution and same concentration is configured, it is then that silver nitrate is molten
Liquid is with hypo solution according to 1:3 ratio correspondence equimolar is mixed to get mixed solution, set aside for use；
B, addition inorganic acid
The a mixed solutions walked are placed its supernatant is taken after a period of time, the mixed solution clarified, then up clearly
Instill a small amount of hydrochloric acid solution in liquid to stir, static placement 6h has gray precipitate things generation in solution during standing；
C, washing
When b step precipitates stabilization, filtering precipitate washing is first washed with deionized and washed again by absolute ethyl alcohol for several times
Afterwards, that is, pure gray precipitate things silver sulfide is obtained；
D, samples dried
Grey silver sulfide obtained by step c is inserted in vacuum drying chamber, drying 5h at 60 DEG C dries, and microsphere diameter is made and exists
1-3um target product.
The inventive method prepares the substantially mechanism of hollow silver sulfide nanometer particles microballoon：Hollow silver sulfide nanometer particles are anti-by interface
It should synthesize, after silver nitrate solution is mixed with hypo solution, mixed liquor is hydrolyzed into vulcanization in alkalescence, sodium thiosulfate
Hydrogen and then hydrolysis S2O3 2-, S2O3 2-With Ag+Reaction generation Ag2(S2O3) complex compound do not generate silver sulfide precipitation, when to mixing
It is in acidity, Ag that solution after slightly inorganic acid is added in solution2(S2O3) complex molecules hydrolysis S2-With Ag+Ion goes forward side by side one
Step reaction generation silver sulfide molecule, these silver sulfide molecules, which are assembled, to form nano particle and particle is connected to form face and reunited
Phenomenon is by silver sulfide roll into hollow silver sulfide nanometer particles microballoon.
Compared with prior art, the beneficial effects of the invention are as follows：The present invention uses liquid-phase precipitation method, with inorganic silver nitrate water
Solution provides silver-colored source, and being hydrolyzed to sulphur source in acid condition with organic sodium thiosulfate participates in generating hollow nanometer with silver ion reaction
Silver sulfide microballoon, this reaction is added without any activating agent and stabilizer, and can to obtain hollow silver sulfide nanometer particles micro- for reaction at room temperature
Ball, its preparation method is simple, and reaction is gentle, consumes energy small, synthesis step is few, simple to operate, to equipment without particular/special requirement, is adapted to big
Large-scale production.It is demonstrated experimentally that obtained is hollow silver sulfide nanometer particles microballoon, a diameter of 1-3um of hollow silver sulfide nanometer particles microballoon
.
The inventive method can obtained various patterns nanometer sulfide, such as：Synthesize CuS nanosheet and nanosphere, Ag2S
Nanosphere and vermiform nano particle, CdS nanosphere and SnS the single inorganic sulphide such as nano particle.Synthesis is completed
Structure determination, the degree of purity that sulfide is made afterwards are good, controllable, and performance is stable.Sulfide and the compound tool of these micro-nano structures
Have been widely used, can be used as the electrode material of the Li/H batteries of height ratio capacity.
The addition and mixing speed of the inorganic acid of above-mentioned b steps.
Below in conjunction with the accompanying drawings and specific embodiment, the present invention is further detailed explanation.
Brief description of the drawings
Fig. 1 is the XRD diffracting spectrums of hollow silver sulfide nanometer particles microballoon prepared by the present invention.
Fig. 2 is hollow silver sulfide nanometer particles microballoon ESEM (SEM) figure prepared by the embodiment of the present invention one.
Fig. 3 is hollow silver sulfide nanometer particles microballoon ESEM (SEM) figure prepared by the embodiment of the present invention two.
Fig. 4 is hollow silver sulfide nanometer particles microballoon ESEM (SEM) figure prepared by the embodiment of the present invention three.
Fig. 5 is hollow silver sulfide nanometer particles microballoon ESEM (SEM) figure prepared by the embodiment of the present invention four.
Embodiment
Embodiment one
The present invention a kind of embodiment be：A kind of preparation method of hollow silver sulfide nanometer particles microballoon, its specific work
Method is：
A, preparation mixed solution
The silver nitrate aqueous solution that 50ml concentration is 0.01M is prepared in beaker container；Again 150ml is prepared in beaker container
Concentration is 0.01M sodium thiosulfate solution；Then silver nitrate solution and hypo solution according to 1:3 ratio pair
Answer equimolar to be mixed to get mixed solution and stand a period of time；
B, addition inorganic acid
The a mixed solutions walked were placed after a period of time and turn supernatant to pour into another beaker, that is clarified is mixed
Solution is closed, the HCl solution 3ml of 0.5M slightly is then instilled into beaker and is stirred rapidly, static placement 6h is being stood
During have gray precipitate things generation in solution；
C, washing
Supernatant is outwelled when the amount that sediment is generated in beaker is basically unchanged and gray precipitate things are washed, and is first used
Deionized water washing washs three times by absolute ethyl alcohol again for several times and can obtain pure gray precipitate things silver sulfide；
D, samples dried
The beaker that will be equipped with grey silver sulfide is put into vacuum drying chamber, and 5h is dried at 60 DEG C can must dry grey vulcanization
Silver-colored sample.
Can be seen that from the XRD in Fig. 1 the XRD ray diffraction peaks of the vermiform silver sulfide nanometer particles prepared with this method with
Its PDF（00-014-0072）Standard card is consistent, can be concluded that the vermiform silver sulfide nanometer particles crystal type belongs to by contrast
Monoclinic system, is also the silver sulfide of acanthite type；There is no any miscellaneous peak in diffraction maximum, illustrate that the degree of purity of the silver sulfide is higher,
Have no other impurities.
Fig. 2 is the scanning electron microscope (SEM) photograph of the hollow silver sulfide nanometer particles microballoon prepared after this example solution left standstill 6h, Ke Yiqing
The clear specific pattern for finding out silver sulfide microballoon：Hollow micron ball and sphere wall thickness is very thin, the hollow silver sulfide microballoon be by
The interconnection of silver sulfide nanometer particles particle is curled into microballoon, and the size of particle is 20nm or so, the hollow silver sulfide microballoon of formation it is straight
Footpath size is 0.8-2.5um.
Embodiment two
The present invention a kind of embodiment be：A kind of preparation method of hollow silver sulfide nanometer particles microballoon, its specific work
Method is：
A, preparation mixed solution
The silver nitrate aqueous solution that 50ml concentration is 0.02M is prepared in beaker container；Again 150ml is prepared in beaker container
Concentration is 0.02M sodium thiosulfate solution；Then silver nitrate solution and hypo solution according to 1:3 ratio pair
Answer equimolar to be mixed to get mixed solution and stand a period of time；
B, addition inorganic acid
The a mixed solutions walked were placed after a period of time and turn supernatant to pour into another beaker, that is clarified is mixed
Solution is closed, the HCl solution 3ml of 0.5M slightly is then instilled into beaker and is stirred rapidly, static placement 6h is being stood
During have gray precipitate things generation in solution；
C, washing
Supernatant is outwelled when the amount that sediment is generated in beaker is basically unchanged and gray precipitate things are washed, and is first used
Deionized water washing washs three times by absolute ethyl alcohol again for several times and can obtain pure gray precipitate things silver sulfide；
D, samples dried
The beaker that will be equipped with grey silver sulfide is put into vacuum drying chamber, and 5h is dried at 60 DEG C can must dry grey vulcanization
Silver-colored sample.
Fig. 3 is the scanning electron microscope (SEM) photograph of the hollow silver sulfide nanometer particles microballoon prepared after this example solution left standstill 6h, Ke Yiqing
The clear specific pattern for finding out silver sulfide：Hollow micron ball and sphere wall thickness is very thin, the hollow silver sulfide microballoon is by nanometer
Vulcanization Argent grain interconnection is curled into microballoon, and the size of particle is 20nm or so, the diameter chi of the hollow silver sulfide microballoon of formation
Very little is 1.0-2.8um.
Embodiment three
The present invention a kind of embodiment be：A kind of preparation method of hollow silver sulfide nanometer particles microballoon, its specific work
Method is：
A, preparation mixed solution
The silver nitrate aqueous solution that 50ml concentration is 0.03M is prepared in beaker container；Again 150ml is prepared in beaker container
Concentration is 0.03M sodium thiosulfate solution；Then silver nitrate solution and hypo solution according to 1:3 ratio pair
Answer equimolar to be mixed to get mixed solution and stand a period of time；
B, addition inorganic acid
The a mixed solutions walked were placed after a period of time and turn supernatant to pour into another beaker, that is clarified is mixed
Solution is closed, the HCl solution 5ml of 0.5M slightly is then instilled into beaker and is stirred rapidly, static placement 6h is being stood
During have gray precipitate things generation in solution；
C, washing
Supernatant is outwelled when the amount that sediment is generated in beaker is basically unchanged and gray precipitate things are washed, and is first used
Deionized water washing washs three times by absolute ethyl alcohol again for several times and can obtain pure gray precipitate things silver sulfide；
D, samples dried
The beaker that will be equipped with grey silver sulfide is put into vacuum drying chamber, and 5h is dried at 60 DEG C can must dry grey vulcanization
Silver-colored sample.
Fig. 4 is the scanning electron microscope (SEM) photograph of the hollow silver sulfide nanometer particles microballoon prepared after this example solution left standstill 6h, Ke Yiqing
The clear specific pattern for finding out silver sulfide microballoon：Hollow microsphere and sphere wall thickness are 100nm or so, the hollow silver sulfide microballoon
It is that microballoon is curled into by the interconnection of silver sulfide nanometer particles particle, the size of particle is 100nm or so, the hollow silver sulfide microballoon of formation
Diameter dimension be 0.5-2.0um.
Example IV
The present invention a kind of embodiment be：A kind of preparation method of hollow silver sulfide nanometer particles microballoon, its specific work
Method is：
A, preparation mixed solution
The silver nitrate aqueous solution that 50ml concentration is 0.04M is prepared in beaker container；Again 150ml is prepared in beaker container
Concentration is 0.04M sodium thiosulfate solution；Then silver nitrate solution and hypo solution according to 1:3 ratio pair
Answer equimolar to be mixed to get mixed solution and stand a period of time；
B, addition inorganic acid
The a mixed solutions walked were placed after a period of time and turn supernatant to pour into another beaker, that is clarified is mixed
Solution is closed, the HCl solution 5ml of 0.5M slightly is then instilled into beaker and is stirred rapidly, static placement 6h is being stood
During have gray precipitate things generation in solution；
C, washing
Supernatant is outwelled when the amount that sediment is generated in beaker is basically unchanged and gray precipitate things are washed, and is first used
Deionized water washing washs three times by absolute ethyl alcohol again for several times and can obtain pure gray precipitate things silver sulfide；
D, samples dried
The beaker that will be equipped with grey silver sulfide is put into vacuum drying chamber, and 5h is dried at 60 DEG C can must dry grey vulcanization
Silver-colored sample.
Fig. 5 is the scanning electron microscope (SEM) photograph of the hollow silver sulfide nanometer particles microballoon prepared after this example solution left standstill 6h, Ke Yiqing
The clear specific pattern for finding out silver sulfide microballoon：Hollow microsphere and sphere wall thickness are 100nm or so, the hollow silver sulfide microballoon
It is that microballoon is curled into by the interconnection of silver sulfide nanometer particles particle, the size of particle is 100nm or so, the hollow silver sulfide microballoon of formation
Diameter dimension be 0.5-2.0um.
Claims (4)
1. a kind of preparation method of hollow silver sulfide nanometer particles microballoon, its specific practice is：
A, preparation mixed solution
Configure the sodium thiosulfate solution of certain density silver nitrate aqueous solution and same concentration, then silver nitrate solution with
Hypo solution is according to 1:3 ratio correspondence equimolar is mixed to get mixed solution, set aside for use；
B, addition inorganic acid
The a mixed solutions walked are placed its supernatant is taken after a period of time, the mixed solution clarified, then up in clear liquid
Instill a small amount of hydrochloric acid solution to stir, static placement 6h has gray precipitate things generation in solution during standing；
C, washing
When b step is precipitated it is stable when, filtering precipitate washing is first washed with deionized for several times again after absolute ethyl alcohol is washed,
Obtain pure gray precipitate things silver sulfide；
D, samples dried
Grey silver sulfide obtained by step c is inserted in vacuum drying chamber, drying 5h at 60 DEG C dries, and microsphere diameter is made in 1-
3um target product.
2. a kind of preparation method of hollow silver sulfide nanometer particles microballoon as claimed in claim 1, it is characterised in that：Described a steps
Silver nitrate aqueous solution and the control of the sodium thiosulfate solution of same concentration are in 0.01-0.05M.
3. a kind of preparation method of hollow silver sulfide nanometer particles microballoon as claimed in claim 1, it is characterised in that：Described b steps
Concentration of hydrochloric acid solution used is 0.5M.
4. a kind of preparation method of hollow silver sulfide nanometer particles microballoon as claimed in claim 1, it is characterised in that：Described c steps
Centrifuge be low-speed centrifugal, to obtain micron ball object.
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| CN110436510B (en) * | 2019-08-13 | 2021-08-10 | 华中科技大学 | Preparation method of water-soluble silver sulfide nanoshell |
| CN113413927A (en) * | 2021-06-18 | 2021-09-21 | 广东广纳安疗科技有限公司 | Method for removing antioxidant sulfite in compound amino acid injection |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101559972A (en) * | 2009-05-07 | 2009-10-21 | 上海交通大学 | Preparation method of silver sulfide nano particle |
| CN101885507A (en) * | 2010-07-30 | 2010-11-17 | 黑龙江大学 | Method for synchronous precipitation and polymeric synthesis of floatable silver sulfide nanocrystalline |
| CN102009172A (en) * | 2010-09-27 | 2011-04-13 | 山东大学 | Resistance switch material in Ag/Ag2S core/shell nanometer structure and preparation method thereof |
| CN104973618A (en) * | 2015-06-15 | 2015-10-14 | 东华大学 | Preparation method for hollow silver sulfide microspheres |
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2016
- 2016-03-21 CN CN201610159431.1A patent/CN105819496B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101559972A (en) * | 2009-05-07 | 2009-10-21 | 上海交通大学 | Preparation method of silver sulfide nano particle |
| CN101885507A (en) * | 2010-07-30 | 2010-11-17 | 黑龙江大学 | Method for synchronous precipitation and polymeric synthesis of floatable silver sulfide nanocrystalline |
| CN102009172A (en) * | 2010-09-27 | 2011-04-13 | 山东大学 | Resistance switch material in Ag/Ag2S core/shell nanometer structure and preparation method thereof |
| CN104973618A (en) * | 2015-06-15 | 2015-10-14 | 东华大学 | Preparation method for hollow silver sulfide microspheres |
Non-Patent Citations (1)
| Title |
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| "具有特殊形貌的金属、硫化物纳米材料的制备";张杰;《中国优秀博硕士学位论文全文数据库（硕士）工程科技I辑》;20060215;第17页-34页 * |
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