CN108373166A - A kind of rodlike SnO2The preparation method and products obtained therefrom of micro nano structure - Google Patents
A kind of rodlike SnO2The preparation method and products obtained therefrom of micro nano structure Download PDFInfo
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- CN108373166A CN108373166A CN201810302535.2A CN201810302535A CN108373166A CN 108373166 A CN108373166 A CN 108373166A CN 201810302535 A CN201810302535 A CN 201810302535A CN 108373166 A CN108373166 A CN 108373166A
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
The invention discloses a kind of stannic oxides of sheet self assembly（SnO2）The preparation method and products obtained therefrom of rodlike micro Nano material, stannic chloride pentahydrate and hydroxylamine hydrochloride are added in hydrochloric acid solution, stir evenly to obtain uniform solution；After uniform solution is transferred to reaction kettle, it is placed at 75 125 DEG C and carries out solvent thermal reaction；It will be calcined in Muffle furnace high temperature after reactant centrifuge washing, obtain rodlike stannic oxide.Present invention is simple, efficient, low raw-material cost, production cost is low, is of great significance to the large-scale industrial production and its practical application of nanometer tin dioxide rod.Products therefrom yield is high, purity is high, pattern is uniform, narrow size distribution, and building-up process is easily controllable, and product morphology is unique, reproducible, obtained rodlike SnO2For micro nano structure in lithium ion battery, photocatalysis removes pollutant, and the fields such as air-sensitive have potential application.
Description
Technical field
The present invention relates to a kind of sheet self assembly SnO2The preparation method and products obtained therefrom of rodlike micro nano structure.
Background technology
Stannic oxide（SnO2）, as a kind of n-type semiconductor, energy gap 3.6ev（In 300K）.SnO2 is micro-nano
Material has unique optics, electric property, surface characteristic and characterization of adsorption, and price is just
Preferably, preparation method is simple, makes it in chemical industry catalysis, gas sensor, coating, pressure sensitive, electricity
The various fields such as pond electrode material and treatment of Organic Wastewater all have a wide range of applications.It is well known that SnO2 is micro-nano
The pattern of material is applied to have a major impact.Related SnO2The preparation of nano material and its be used for gas sensitive and electrode material
The research in the fields such as material has had a large amount of reports.Recent decades, it is more that researcher has used different methods successfully to prepare
The SnO of kind pattern2Nano material, such as：Nanotube, nanobelt, nanometer sheet, nano flower, nano cubic, hollow ball, octahedron,
Nanometer rods, nano wire, nanometer stick array etc..
YanZhao,JingyuanLiu,QiLiu,YanboSun,DaleiSong,WanluYang,JunWanga,
LianheLiu is reported in 136,1 December 2014 of Materials Letters.Volume, Pages 286-288
SnO has been synthesized by one-step calcination method2Hollow ball has preferable air-sensitive property to ethyl alcohol.NaLi,HuaweiSong,
HaoCui, ChengxinWang are in 130,1 June 2014 of Electrochimica Acta.Volume, Pages 670-
Uniform deposition SnO on graphene is reported in 6782Nano particle has preferable lithium electrical effect.Hsyi-EnChengDe-
CihTianKuan-ChunHuang is in Procedia Engineering.Volume 36,2012, Pages 510-515
Report is prepared for SnO2 nanometer sheets by the method for atomic layer deposition, the photoelectric conversion result having had.
In conclusion people have used vapor phase method, liquid phase method and solid phase method successfully to prepare SnO2Nano-particle, nanometer
Line, nanobelt, nanometer rods, nanotube, nano column array, nanometer sheet, hollow ball, flower-like structure, nanofiber, octahedron, sky
The nanostructure of the different-shapes such as the heart cube.The SnO of different-shape2Nano-particle shows unique property, is passed in air-sensitive
The fields such as sensor, electrode material, chemical industry catalysis, coating, pressure sensitive, water treatment, degradation of organic substances have important application
Value.Wherein, monodimension nano stick can promote electronics fast transfer and increase more active sites due to its high aspect ratio,
It is of increased attention.And SnO2Club shaped structure is typically all to be prepared by method of electrostatic spinning, by simple molten
The SnO of sheet self assembly prepared by the hot method of agent2Rodlike micro nano structure or few articles report.
Invention content
The present invention provides a kind of rodlike SnO for deficiency existing for existing method2The preparation method of micro nano structure,
This method has the advantages such as raw material sources are extensive, synthesis technology is easy, easily operated, product morphology is reproducible, size adjustable.
Present invention combination solvent-thermal method and calcination method have obtained rodlike SnO2Micro nano structure, specific technical solution are as follows：
A kind of rodlike SnO2The preparation method of micro nano structure, this approach includes the following steps：
（1）By stannic chloride pentahydrate（SnCl4·5H2O）It is added in hydrochloric acid solution with hydroxylamine hydrochloride, stirs evenly uniform molten
Liquid；
（2）After uniform solution is transferred to reaction kettle, it is placed at 75-125 DEG C and carries out thermal response；
（3）It will be calcined in Muffle furnace high temperature after reactant centrifuge washing, obtain rodlike stannic oxide.
The present invention prepares rodlike SnO by the combination of solvent-thermal method and calcination method2Micro nano structure, side through the invention
Method can be easily obtained rodlike SnO2, the rodlike SnO of gained2A diameter of 300-500 nm, draw ratio 6-20.
Above-mentioned steps（1）In, the molar ratio of hydroxylamine hydrochloride and water stannic chloride is 1：6.6-7.2；Hydrochloric acid solution volume is
A concentration of 0.1mol/L of 70ml；Mixing time is 30min.
Above-mentioned steps（2）In, reaction kettle size is 100mL；A length of 8-16h when thermal response in reaction kettle.
Above-mentioned steps（3）In, step（3）In, Muffle furnace high temperature calcination temperature is 500-600 DEG C；Heating rate is 5
℃/min；A length of 2-4h when calcining.
The method of the present invention is summarized on the basis of a large amount of compound experiments, SnO2The microscopic appearance identification of product
Height prepares SnO with the other methods reported both at home and abroad2There are greatest differences for structure, and operation controllability is good, and products collection efficiency is high.
The micro nano structure that the present invention obtains is rodlike, by the SnO being connected with each other2Particle assembles.It is prepared by the invention
Simple for process, efficient, low raw-material cost, production cost be low, to the large-scale industrial production of stannic oxide nanometer side and its
Practical application is of great significance.Products therefrom yield is high, purity is high, pattern is uniform, narrow size distribution, and building-up process is easy to control
System, product morphology is unique, reproducible, obtained rodlike SnO2Micro nano structure in lithium ion battery, go to decontaminate by photocatalysis
Object is contaminated, the fields such as air-sensitive have potential application.
The present invention has obtained rodlike SnO by solvent-thermal method and calcination method2Micro nano structure, pattern is special, the present invention
Products obtained therefrom is also within the scope of the present invention.
Description of the drawings
Fig. 1 is the rodlike SnO that the embodiment of the present invention 1 synthesizes2The scanning electron microscope of structure（SEM）Picture.
Fig. 2 is the rodlike SnO that the embodiment of the present invention 1 synthesizes2The X ray diffracting spectrum of structure（XRD）.
Fig. 3 is the rodlike SnO that the embodiment of the present invention 3 synthesizes2The scanning electron microscope of structure（SEM）Picture.
Fig. 4 is the SnO that the present invention implements that comparative example 1 synthesizes2The scanning electron microscope of structure（SEM）Picture.
Fig. 5 is the SnO that the present invention implements that comparative example 3 synthesizes2The scanning electron microscope of structure（SEM）Picture.
Specific implementation mode
Below by embodiment, the present invention will be further elaborated, and following the description is only for explaining the present invention, not
Its content is defined.
Embodiment 1
1.1 by 0.35g stannic chloride pentahydrates（SnCl4·5H2O）It is added to a concentration of 0.1mol/L of 70mL with 0.01g hydroxylamine hydrochlorides
Hydrochloric acid solution in, stirring 30min obtain uniform solution；
1.2 are transferred to above-mentioned solution in 100mL reaction kettles, and 12 h are reacted at 100 DEG C；
1.3 after reaction, and by centrifuging and washing, then the Muffle furnace high temperature at 550 DEG C is calcined（Heating rate 5
℃/min）3 hours, a diameter of 400-500 nm are obtained, draw ratio is the rodlike stannic oxide of 7-14.The SEM figures of product are as schemed
Shown in 1, it can be seen from the figure that products obtained therefrom pattern is regular, single.The XRD diagram of product is as shown in Fig. 2, XRD results and standard
XRD cards（41-1445）It is consistent, it was demonstrated that the crystalline phase of products therefrom is SnO2Phase.
Embodiment 2
2.1 by 0.69g stannic chloride pentahydrates（SnCl4·5H2O）It is added to a concentration of 0.1mol/L of 70mL with 0.02g hydroxylamine hydrochlorides
Hydrochloric acid solution in, stirring 35min obtain uniform solution；
2.2 are transferred to above-mentioned solution in 100mL reaction kettles, and 10 h are reacted at 110 DEG C；
2.3 after reaction, and by centrifuging and washing, then the Muffle furnace high temperature at 520 DEG C is calcined（Heating rate 5
℃/min）3 hours, a diameter of 300-450 nm are obtained, draw ratio is the rodlike stannic oxide of 7-17.
Embodiment 3
3.1 by 1.38g stannic chloride pentahydrates（SnCl4·5H2O）It is added to a concentration of 0.1mol/L of 70mL with 0.04g hydroxylamine hydrochlorides
Hydrochloric acid solution in, stirring 50min obtain uniform solution；
3.2 are transferred to above-mentioned solution in 100mL reaction kettles, and 13 h are reacted at 90 DEG C；
3.3 after reaction, and by centrifuging and washing, then the Muffle furnace high temperature at 570 DEG C is calcined（Heating rate 5
℃/min）3 hours, the SEM of products therefrom schemed as shown in figure 3, it can be seen from the figure that products obtained therefrom is by SnO2Particle is constituted
Club, rough surface is uniform product appearance, regular, and diameter is between 350-500 nm.
Embodiment 4
4.1 by 0.98g stannic chloride pentahydrates（SnCl4·5H2O）It is added to a concentration of 0.1mol/L of 70mL with 0.02g hydroxylamine hydrochlorides
Hydrochloric acid solution in, stirring 35min obtain uniform solution；
4.2 are transferred to above-mentioned solution in 100mL reaction kettles, and 15 h are reacted at 120 DEG C；
4.3 after reaction, and by centrifuging and washing, then the Muffle furnace high temperature at 550 DEG C is calcined（Heating rate 5
℃/min）4 hours, a diameter of 400-500 nm are obtained, draw ratio is the rodlike stannic oxide of 9-20.
Embodiment 5
5.1 by 2.25g stannic chloride pentahydrates（SnCl4·5H2O）It is added to a concentration of 0.1mol/L of 70mL with 0.07g hydroxylamine hydrochlorides
Hydrochloric acid solution in, stirring 35min obtain uniform solution；
5.2 are transferred to above-mentioned solution in 100mL reaction kettles, and 15 h are reacted at 120 DEG C；
5.3 after reaction, and by centrifuging and washing, then the Muffle furnace high temperature at 550 DEG C is calcined（Heating rate 5
℃/min）4 hours, a diameter of 400-500 nm are obtained, draw ratio is the rodlike stannic oxide of 9-20.
Comparative example 1
1.1 by 0.27g stannic chloride pentahydrates（SnCl4·5H2O）It is added to a concentration of 0.1mol/L of 70mL with 0.01g hydroxylamine hydrochlorides
Hydrochloric acid solution in, stirring 30min obtain uniform solution；
1.2 the same as embodiment 1.
1.3 the same as embodiment 1.
The SEM of products therefrom schemes as shown in figure 4, it can be seen from the figure that products therefrom is that Size Distribution is inhomogenous, reunites
The apparent SnO of phenomenon2Continuous structure pattern, diameter of movement distribution is big, bad dispersibility.The product no longer has rodlike SnO2
Structure structure.
Comparative example 2
2.1 by 1.32g stannic chloride pentahydrates（SnCl4·5H2O）It is added to a concentration of 0.1mol/L of 70mL with 0.05g hydroxylamine hydrochlorides
Hydrochloric acid solution in, stirring 37min obtain uniform solution；
2.2 are transferred to above-mentioned solution in 100mL reaction kettles, and 10 h are reacted at 80 DEG C；
2.3 after reaction, and by centrifuging and washing, then the Muffle furnace high temperature at 550 DEG C is calcined（Heating rate 5
℃/min）2 hours, products therefrom microscopic appearance was that particle and one-dimentional structure coexist.
Comparative example 3
3.1 by 0.27g stannic chloride pentahydrates（SnCl4·5H2O）It is added to a concentration of 0.1mol/L of 70mL with 0.01g hydroxylamine hydrochlorides
Hydrochloric acid solution in, stirring 30min obtain uniform solution；
3.2 the same as embodiment 3.
3.3 the same as embodiment 3.
The SEM of products therefrom scheme as shown in figure 5, it can be seen from the figure that products therefrom be laminated structure, surface it is smooth,
Bad dispersibility.The product no longer has rodlike SnO2Structure structure.
Claims (8)
1. a kind of rodlike stannic oxide（SnO2）The preparation method of micro nano structure, it is characterized in that including the following steps：
（1）By stannic chloride pentahydrate（SnCl4·5H2O）It is added in hydrochloric acid solution with hydroxylamine hydrochloride, stirs evenly to obtain uniform solution；
（2）After uniform solution is transferred to reaction kettle, it is placed at 70-130 DEG C and carries out solvent thermal reaction；
（3）It will be calcined in Muffle furnace high temperature after reactant centrifuge washing, obtain rodlike stannic oxide.
2. preparation method according to claim 1, it is characterized in that：Step（1）In, hydroxylamine hydrochloride and stannic chloride pentahydrate rub
You are than being 1：6.6-7.2；Hydrochloric acid solution volume is a concentration of 0.1mol/L of 70ml；Mixing time is 30-60min.
3. according to claim 1-2 any one of them preparation methods, it is characterized in that：Step（2）In, reaction kettle size is
100mL；A length of 8-16h when thermal response in reaction kettle.
4. preparation method according to claim 1,2 or 3, it is characterized in that：Step（3）In, Muffle furnace high temperature calcining temperature
Degree is 500-600 DEG C；Heating rate is 5 DEG C/min；A length of 2-4h when calcining.
5. according to the preparation method described in any one of claim 1-4, it is characterized in that：Solvent thermal reaction in confined conditions into
Row.
6. preparation method according to any one of claims 1-5, it is characterized in that：Gained SnO2Micro nano structure be it is rodlike,
By the SnO being connected with each other2Particle assembles, SnO2The pattern of particle is disc-shaped structure, and grain size is 50-100 nm.
7. preparation method according to any one of claims 1-5, it is characterized in that：The rodlike SnO of gained2Micro nano structure direct
Diameter is 300-500nm, draw ratio 6-22.
8. according to the rodlike SnO described in any one of claim 1-52Rodlike SnO made from the preparation method of micro nano structure2
Micro nano structure.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113135589A (en) * | 2021-04-26 | 2021-07-20 | 浙江大学 | Vermicular tin oxide gas-sensitive material, preparation method thereof and application of vermicular tin oxide gas-sensitive material in ethanol detection |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1804149A (en) * | 2005-12-01 | 2006-07-19 | 华中师范大学 | SnO2 monodisperse nano monocrystal with square structure and synthesis method thereof |
| CN101565200A (en) * | 2009-06-04 | 2009-10-28 | 西北稀有金属材料研究院 | Preparation of diameter and shape controllable nano tin oxide powder |
| CN106811833A (en) * | 2017-02-16 | 2017-06-09 | 济南大学 | A kind of preparation method of SnO2 micro nanometer fibers |
-
2018
- 2018-04-05 CN CN201810302535.2A patent/CN108373166A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1804149A (en) * | 2005-12-01 | 2006-07-19 | 华中师范大学 | SnO2 monodisperse nano monocrystal with square structure and synthesis method thereof |
| CN101565200A (en) * | 2009-06-04 | 2009-10-28 | 西北稀有金属材料研究院 | Preparation of diameter and shape controllable nano tin oxide powder |
| CN106811833A (en) * | 2017-02-16 | 2017-06-09 | 济南大学 | A kind of preparation method of SnO2 micro nanometer fibers |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113135589A (en) * | 2021-04-26 | 2021-07-20 | 浙江大学 | Vermicular tin oxide gas-sensitive material, preparation method thereof and application of vermicular tin oxide gas-sensitive material in ethanol detection |
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