CN104528808A - Preparation method of hollow tin dioxide microsphere - Google Patents
Preparation method of hollow tin dioxide microsphere Download PDFInfo
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- CN104528808A CN104528808A CN201410833821.3A CN201410833821A CN104528808A CN 104528808 A CN104528808 A CN 104528808A CN 201410833821 A CN201410833821 A CN 201410833821A CN 104528808 A CN104528808 A CN 104528808A
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- tindioxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
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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 discloses a preparation method of a hollow tin dioxide microsphere and belongs to the technical field of preparation of nanomaterials. The preparation method of the hollow tin dioxide microsphere comprises the following steps: (1) weighing NaOH and SnCl2.2H2O at a molar ratio of 1:(0.1-20), dissolving NaOH and SnCl2.2H2O in an organic solvent, mixing uniformly to obtain a mixed solution, and stirring the mixed solution fully and uniformly to obtain a precursor reaction solution, wherein 0.1-1mL of the organic solvent is added into every 0.1mmol of NaOH; (2) carrying out hydrothermal reaction on the precursor reaction solution for 12-48 hours at the temperature of 120-200 DEG C, cooling, and centrifuging; and (3) washing precipitate obtained during centrifuging, and drying to obtain the hollow tin dioxide microsphere. The hollow tin dioxide microsphere is prepared by carrying out hydrothermal reaction, and the preparation process of the hollow tin dioxide microsphere has the advantages of simple flow and moderate condition, does not need special process equipment and is suitable for industrial production.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, be specifically related to a kind of preparation method of tindioxide hollow microsphere.
Background technology
Tindioxide (SnO
2) be a kind of important semiconductor transducer material [Yootana Pimtong-Ngama, Sirithan Jiemsirilersb, Sitthisuntorn Supothina, Preparation of tungsten oxide – tinoxide nanocomposites and their ethylene sensing characteristics, [J] Sensors andActuators A:Physical, 139 (2007) 7-11], the gas sensor prepared with it is highly sensitive, be widely used in various inflammable gas, environmental pollution gas, the detection of industrial gaseous waste and obnoxious flavour and forecast.Meanwhile, SnO
2also can be used as the electrode materials of lithium ion/sodium-ion battery, it has good chemical property [Zhigang Wen, Feng Zheng, Hongchun Yu, Ziran Jiang, KanglianLiu, Hydrothermal synthesis of flowerlike SnO
2nanorod bundles and theirapplication for lithium ion battery, [J] Materials Characterization 76 (2013) 1 – 5].
At present, the preparation method of the tindioxide proposed both at home and abroad mainly contains solid-state chemical reaction method method, sol-gel method, chemical precipitation method and hydrothermal synthesis method.Although solid phase synthesis process technique is simple, its sintering temperature is higher, and soaking time is longer, and product morphology is wayward.Sol-gel method required equipment is simple, and operation is easy to control, but the treatment time is longer, and the gel obtained not easily washs.Precipitator method equipment and process is simple, and cost is low, is easy to suitability for industrialized production, but the greatest problem existed in preparation process is SnO
2the reunion of ultrafine powder.And hydrothermal synthesis reaction carries out at high temperature under high pressure, can effectively suppress the heat of powder in the thermal treatments such as drying and roasting to increase after hydrothermal treatment consists, the particle size of preparation is even, and degree of crystallinity is high, and crystalline state is complete, pattern comparison rule, has higher sintering activity.But prior art is that SnO prepared by starting material with muriate
2maximum difficulty is difficult to remove the chlorion in presoma, result in the reduction of product purity, certain influence [Gao Sainan is caused to its performance, Yuan Gaoqing, Jiang Huanfeng. tin grain oxidation-water heat transfer nano-stannic oxide Liao Shi army, [J] electronic component and material 12 (2006) 57-62].
Summary of the invention
The object of the present invention is to provide a kind of preparation method of tindioxide hollow microsphere, the method is simple to operate, production cost is low, and repeatability is high, be applicable to suitability for industrialized production, the tindioxide hollow microsphere crystal property obtained through present method is good, and purity is high, pattern and size controlled.
The present invention is achieved through the following technical solutions:
A preparation method for tindioxide hollow microsphere, comprises the following steps:
1) by 1:(0.1 ~ 20) mol ratio, get NaOH and SnCl
22H
2o, is dissolved in organic solvent, and mixing obtains mixing solutions, is stirred by this mixing solutions, obtains reaction precursor liquid; Wherein, the add-on of described organic solvent is that every 0.1mmoL NaOH adds 0.1 ~ 1mL organic solvent;
2) by reaction precursor liquid at 120 ~ 200 DEG C, hydro-thermal reaction 12 ~ 48h, cooling after centrifugal;
3) drying is carried out, obtained tindioxide hollow microsphere by after the centrifugal precipitation cleaning obtained.
In mixing solutions, the concentration of NaOH is 0.01 ~ 1mol/L; SnCl
22H
2the concentration of O is 0.05 ~ 2mol/L.
Described organic solvent is ethanol, ethylene glycol or glycerol.
Step 1) described in stir be by mixing solutions magnetic agitation 10 ~ 120min.
Step 2) described in hydro-thermal reaction be that the hydrothermal reaction kettle be placed in using tetrafluoroethylene as liner carries out by reaction precursor liquid, the packing ratio of hydrothermal reaction kettle used is 30% ~ 70%.
Step 3) described in cleaning be by the centrifugal precipitation obtained successively through washed with de-ionized water 1 ~ 5 time, washes of absolute alcohol 1 ~ 3 time.
Step 3) described in drying be by cleaning after be deposited in 50 ~ 90 DEG C at dry 1 ~ 5h.
Obtained tindioxide hollow microsphere is by diameter to be diameter that 10 ~ 50nm nanometer rod is formed the be hollow microsphere of 5 ~ 8 μm.
Compared with prior art, the present invention has following useful technique effect:
The present invention is with NaOH and SnCl
22H
2o is raw material, adopts hydrothermal method to prepare tindioxide hollow microsphere, efficiently avoid the muriatic appearance of indissoluble in product.And the present invention can by controlling the SnCl in reaction process
2: the mol ratio of NaOH, the time of hydro-thermal reaction and temperature regulate pattern and the size of product, make the product prepared have higher purity.The inventive method preparation technology flow process is simple, and condition is moderate, does not need special processing unit, be easy to suitability for industrialized production, the tindioxide hollow microsphere crystal property obtained through the present invention is good, and purity is high, pattern and size controlled, avoid the particle aggregation that high-temperature roasting causes.
Accompanying drawing explanation
Fig. 1 is SnO prepared by the present invention
2x-ray diffractogram.
Fig. 2 is SnO prepared by the present invention
2flied emission shape appearance figure; Wherein, (a) is the Flied emission shape appearance figure under 11.0k; B () is the Flied emission shape appearance figure under 22.0k.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, and the explanation of the invention is not limited.
Embodiment 1
A preparation method for tindioxide hollow microsphere, comprises the following steps:
1) prepare 50mL 0.05mol/L NaOH, take 0.06mol SnCl
22H
2o dissolves in wherein, adds 10ml ethylene glycol, and mixing obtains mixing solutions, and by mixing solutions at normal temperatures, magnetic agitation 10min, obtains reaction precursor liquid;
2) by reaction precursor liquid at 150 DEG C, hydro-thermal reaction 12h, centrifugal after naturally cooling;
Described hydro-thermal reaction is that the hydrothermal reaction kettle be placed in using tetrafluoroethylene as liner carries out by reaction precursor liquid, and the packing ratio of hydrothermal reaction kettle used is 30% ~ 70%;
3) by the centrifugal precipitation obtained successively through washed with de-ionized water 1 ~ 5 time, washes of absolute alcohol 1 ~ 3 time, dry 4h at 60 DEG C, obtains tindioxide hollow microsphere afterwards;
Can reflect that the product obtained by the present invention is tindioxide by Fig. 1, product crystallinity is better.This tindioxide microballoon is hollow structure as can be seen from Figure 2, is by diameter to be diameter that 50nm nano wire is formed the be microballoon of 7 μm.
Embodiment 2
A preparation method for tindioxide hollow microsphere, comprises the following steps:
1) prepare 30mL 0.04mol/L NaOH, take 0.02mol SnCl
22H
2o dissolves in wherein, adds 18ml ethanol, and mixing obtains mixing solutions, and by mixing solutions at normal temperatures, magnetic agitation 20min, obtains reaction precursor liquid;
2) by reaction precursor liquid at 170 DEG C, hydro-thermal reaction 18h, centrifugal after naturally cooling;
Described hydro-thermal reaction is that the hydrothermal reaction kettle be placed in using tetrafluoroethylene as liner carries out by reaction precursor liquid, and the packing ratio of hydrothermal reaction kettle used is 30% ~ 70%;
3) by the centrifugal precipitation obtained successively through washed with de-ionized water 3 times, washes of absolute alcohol 2 times, dry 4h at 70 DEG C, obtains tindioxide hollow microsphere afterwards;
The tindioxide hollow microsphere that this example obtains is by diameter to be diameter that 25nm nano wire is formed the be microballoon of 5 μm.
Embodiment 3
A preparation method for tindioxide hollow microsphere, comprises the following steps:
1) prepare 35mL 0.07mol/L NaOH, take 0.03mol SnCl
22H
2o dissolves in wherein, adds 25ml glycerol, and mixing obtains mixing solutions, and by mixing solutions at normal temperatures, magnetic agitation 30min, obtains reaction precursor liquid;
2) by reaction precursor liquid at 160 DEG C, hydro-thermal reaction 28h, centrifugal after naturally cooling;
Described hydro-thermal reaction is that the hydrothermal reaction kettle be placed in using tetrafluoroethylene as liner carries out by reaction precursor liquid, and the packing ratio of hydrothermal reaction kettle used is 30% ~ 70%;
3) by the centrifugal precipitation obtained successively through washed with de-ionized water 2 times, washes of absolute alcohol 1 time, dry 5h at 50 DEG C, obtains tindioxide hollow microsphere afterwards;
The tindioxide hollow microsphere that this example obtains is by diameter to be diameter that 40nm nano wire is formed the be microballoon of 6 μm.
Embodiment 4
A preparation method for tindioxide hollow microsphere, comprises the following steps:
1) prepare 40mL 0.03mol/L NaOH, take 0.04mol SnCl
22H
2o dissolves in wherein, adds 15ml ethanol, and mixing obtains mixing solutions, and by mixing solutions at normal temperatures, magnetic agitation 80min, obtains reaction precursor liquid;
2) by reaction precursor liquid at 160 DEG C, hydro-thermal reaction 12h, centrifugal after naturally cooling;
Described hydro-thermal reaction is that the hydrothermal reaction kettle be placed in using tetrafluoroethylene as liner carries out by reaction precursor liquid, and the packing ratio of hydrothermal reaction kettle used is 30% ~ 70%;
3) by the centrifugal precipitation obtained successively through washed with de-ionized water 2 times, washes of absolute alcohol 1 time, dry 4h at 50 DEG C, obtains tindioxide hollow microsphere afterwards;
The tindioxide hollow microsphere that this example obtains is by diameter to be diameter that 30nm nano wire is formed the be microballoon of 8 μm.
Embodiment 5
A preparation method for tindioxide hollow microsphere, comprises the following steps:
1) prepare 50mL 0.09mol/L NaOH, take 0.1mol SnCl
22H
2o dissolves in wherein, adds 25ml ethylene glycol, and mixing obtains mixing solutions, and by mixing solutions at normal temperatures, magnetic agitation 120min, obtains reaction precursor liquid;
2) by reaction precursor liquid at 190 DEG C, hydro-thermal reaction 18h, centrifugal after naturally cooling;
Described hydro-thermal reaction is that the hydrothermal reaction kettle be placed in using tetrafluoroethylene as liner carries out by reaction precursor liquid, and the packing ratio of hydrothermal reaction kettle used is 30% ~ 70%;
3) by the centrifugal precipitation obtained successively through washed with de-ionized water 1 time, washes of absolute alcohol 3 times, dry 1h at 90 DEG C, obtains tindioxide hollow microsphere afterwards;
The tindioxide hollow microsphere that this example obtains is by diameter to be diameter that 20nm nano wire is formed the be microballoon of 6 μm.
Claims (8)
1. a preparation method for tindioxide hollow microsphere, is characterized in that, comprises the following steps:
1) by 1:(0.1 ~ 20) mol ratio, get NaOH and SnCl
22H
2o, is dissolved in organic solvent, and mixing obtains mixing solutions, is stirred by this mixing solutions, obtains reaction precursor liquid; Wherein, the add-on of described organic solvent is that every 0.1mmoL NaOH adds 0.1 ~ 1mL organic solvent;
2) by reaction precursor liquid at 120 ~ 200 DEG C, hydro-thermal reaction 12 ~ 48h, cooling after centrifugal;
3) drying is carried out, obtained tindioxide hollow microsphere by after the centrifugal precipitation cleaning obtained.
2. the preparation method of a kind of tindioxide hollow microsphere according to claim 1, is characterized in that, in mixing solutions, the concentration of NaOH is 0.01 ~ 1mol/L; SnCl
22H
2the concentration of O is 0.05 ~ 2mol/L.
3. the preparation method of a kind of tindioxide hollow microsphere according to claim 1, is characterized in that, described organic solvent is ethanol, ethylene glycol or glycerol.
4. the preparation method of a kind of tindioxide hollow microsphere according to claim 1, is characterized in that, step 1) described in stir be by mixing solutions magnetic agitation 10 ~ 120min.
5. the preparation method of a kind of tindioxide hollow microsphere according to claim 1, it is characterized in that, step 2) described in hydro-thermal reaction be that the hydrothermal reaction kettle be placed in using tetrafluoroethylene as liner carries out by reaction precursor liquid, the packing ratio of hydrothermal reaction kettle used is 30% ~ 70%.
6. the preparation method of a kind of tindioxide hollow microsphere according to claim 1, is characterized in that, step 3) described in cleaning be by the centrifugal precipitation obtained successively through washed with de-ionized water 1 ~ 5 time, washes of absolute alcohol 1 ~ 3 time.
7. the preparation method of a kind of tindioxide hollow microsphere according to claim 1, is characterized in that, step 3) described in drying be by cleaning after be deposited in 50 ~ 90 DEG C at dry 1 ~ 5h.
8. the preparation method of a kind of tindioxide hollow microsphere according to claim 1, is characterized in that, obtained tindioxide hollow microsphere is by diameter to be diameter that 10 ~ 50nm nanometer rod is formed the be hollow microsphere of 5 ~ 8 μm.
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| CN201410833821.3A CN104528808B (en) | 2014-12-27 | 2014-12-27 | A kind of preparation method of tin ash hollow microsphere |
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| CN201410833821.3A CN104528808B (en) | 2014-12-27 | 2014-12-27 | A kind of preparation method of tin ash hollow microsphere |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105329937A (en) * | 2015-11-09 | 2016-02-17 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing stannic oxide nanometer microspheres through supercritical method |
| CN105514404A (en) * | 2016-01-25 | 2016-04-20 | 陕西科技大学 | Nanoparticle assembled burr spherical SnO2 sodium-ion battery anode material and preparation method thereof |
| CN105514405A (en) * | 2016-01-25 | 2016-04-20 | 陕西科技大学 | Particle-assembled cauliflower-shaped SnO2 sodium-ion battery cathode material and preparation method thereof |
| CN105529455A (en) * | 2016-01-25 | 2016-04-27 | 陕西科技大学 | Prismatic assembly ball shaped SnO2 sodium-ion battery anode material and preparation method thereof |
| CN105552351A (en) * | 2016-01-25 | 2016-05-04 | 陕西科技大学 | Nano-particle-assembled spherical SnO2 sodium-ion battery cathode material and preparation method thereof |
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| CN101823703A (en) * | 2009-03-06 | 2010-09-08 | 中国科学院宁波材料技术与工程研究所 | Controllable preparation method for petaliform tin oxide nano powder |
| CN102086044A (en) * | 2009-12-03 | 2011-06-08 | 中国科学院宁波材料技术与工程研究所 | Method for preparing hollow spherical stannic oxide nano powder |
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2014
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101823703A (en) * | 2009-03-06 | 2010-09-08 | 中国科学院宁波材料技术与工程研究所 | Controllable preparation method for petaliform tin oxide nano powder |
| CN102086044A (en) * | 2009-12-03 | 2011-06-08 | 中国科学院宁波材料技术与工程研究所 | Method for preparing hollow spherical stannic oxide nano powder |
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| LI YUE ET AL.: ""Selective synthesis of SnO2 hollow microspheres and nano-sheets via a hydrothermal route"", 《MATERIALS CHEMISTRY》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105329937A (en) * | 2015-11-09 | 2016-02-17 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing stannic oxide nanometer microspheres through supercritical method |
| CN105514404A (en) * | 2016-01-25 | 2016-04-20 | 陕西科技大学 | Nanoparticle assembled burr spherical SnO2 sodium-ion battery anode material and preparation method thereof |
| CN105514405A (en) * | 2016-01-25 | 2016-04-20 | 陕西科技大学 | Particle-assembled cauliflower-shaped SnO2 sodium-ion battery cathode material and preparation method thereof |
| CN105529455A (en) * | 2016-01-25 | 2016-04-27 | 陕西科技大学 | Prismatic assembly ball shaped SnO2 sodium-ion battery anode material and preparation method thereof |
| CN105552351A (en) * | 2016-01-25 | 2016-05-04 | 陕西科技大学 | Nano-particle-assembled spherical SnO2 sodium-ion battery cathode material and preparation method thereof |
| CN105529455B (en) * | 2016-01-25 | 2018-07-17 | 陕西科技大学 | A kind of spherical SnO of prism assembling2Anode material of lithium-ion battery and preparation method thereof |
| CN105514405B (en) * | 2016-01-25 | 2018-08-24 | 陕西科技大学 | A kind of particle assembling cauliflower-shaped SnO2Anode material of lithium-ion battery and preparation method thereof |
| CN105514404B (en) * | 2016-01-25 | 2018-08-24 | 陕西科技大学 | A kind of spherical SnO of nano particle assembling burr2Anode material of lithium-ion battery and preparation method thereof |
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