CN102627316A - Preparation method for SnO2 three-dimensional hollow sphere nano material - Google Patents
Preparation method for SnO2 three-dimensional hollow sphere nano material Download PDFInfo
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- CN102627316A CN102627316A CN2012101193604A CN201210119360A CN102627316A CN 102627316 A CN102627316 A CN 102627316A CN 2012101193604 A CN2012101193604 A CN 2012101193604A CN 201210119360 A CN201210119360 A CN 201210119360A CN 102627316 A CN102627316 A CN 102627316A
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Abstract
The invention relates to a preparation method for a SnO2 three-dimensional hollow sphere nano material and belongs to the field of preparation processes of materials. The preparation method is characterized by comprising the following steps of: firstly, adding concentrated hydrochloric acid in tin powder drop by drop and stirring; secondly, adding absolute ethyl alcohol; transferring a white solution to a reaction kettle; sealing the reaction kettle and then carrying out a hydrothermal reaction; and finally, carrying out repeated high-speed centrifugal separation, water washing and alcohol washing to obtain white powder. The white powder is a SnO2 three-dimensional hollow sphere formed by self-assembling and directionally collecting SnO2 nanorods; the average diameter of the hollow sphere is 190nm; the thickness of the outer wall is 50nm; the size of crystal grains is about 12nm; and the crystal grains are regular in appearance, distinct in outline and uniform in dispersion. According to the preparation method disclosed by the invention, no surfactant or temperate for assisting is needed; no toxic or harmful organic solvent is used; the used raw materials are low in price and easily-accessible; and the preparation method is easy in operation and is an environment-friendly preparation method.
Description
Technical field
The invention belongs to the material preparation process field, relate to a kind of SnO
2Three-dimensional hollow ball preparation of nanomaterials, particularly a kind of single step hydrothermal preparing process.
Background technology
SnO
2Be that a kind of energy gap is the n type direct band-gap semicondictor of 3.6eV; Owing to have better chemical and thermostability; Reducing gas had responsive irritability; And self special electronic structure---saturated valence band and empty conduction band makes it at aspects such as air-sensitive and bio-sensing, lithium cell cathode material, sensitization solar battery, photoelectron original paper, catalyzer wide application potential arranged.
Research for many years shows that nano material has the special performance that obviously is different from unit molecule and block materials; And scholars generally believe that also size and the pattern of material and the physics of himself, chemistry, optics and catalytic property are closely bound up, so design construction clean cut, size rule, pattern are controlled, dispersiveness SnO preferably
2Nano material, like monodimension nano stick, nano wire, nanotube, two-dimensional nano sheet, multilayer film, three-dimensional structure has caused countries in the world scientific workers' concern.The three-dimensional structure that wherein assembles by low Wei Nami construction unit, help gas molecule dispersive porous surface because of it has, help to adsorb more gas molecule be worth special concern than bigger serface, stronger adsorptive power, outstanding stability.
Relevant in recent years SnO
2Three-dimensional nanometer material preparation and the report of using are extensive.People such as H.K.Wang (H.K.Wang, F.Fu, F.H.Zhang, H.E.Wang, S.V.Kershaw, J.Q.Xu, S.G.Sun and A.L.Rogach, J.Mater.Chem.2012,22,2140) are with NH
4F or NaF are the morphology control agent, and non-template method hydro-thermal has been synthesized micron order SnO
2That solid sphere and hollow ball, advantage are is easy to operate, cost is low, but the diameter of ball is bigger, and pattern is irregular, and agglomeration is serious; People such as F.Gyger (F.Gyger, M.H ü bner, C.Feldmann; N.Barsan and U.Weimar, Chem.Mater.2010,22; 4821) be tensio-active agent with Trimethyllaurylammonium bromide (CTAB); With hexanol as cosurfactant, with n-dodecane as oil phase, with Sn (Ot-Bu)
4As SnO
2Presoma, as reaction terminating agent, synthesized nano level SnO with terepthaloyl moietie through microemulsion method
2Hollow ball, advantage are that the size of ball has only several nanometers, be uniformly dispersed, but mostly starting material are organic solvent, and use tensio-active agent in a large number, not environmental protection of preparation method; People such as X.M.Yin (X.M.Yin, C.C.Li, M.Zhang, Q.Y.Hao, S.Liu, Q.H.Li, L.B.Chen and T.H.Wang, Nanotechnology, 2009,20,455503) are template with the carbon ball, with hydrothermal method with Sn (OH)
4Pre precipitation is removed template through calcining on template at last, thereby obtains SnO
2Hollow ball, schedule of operation is loaded down with trivial details, and wastes resource, the energy.At present, with common nontoxic starting material as SnO
2Precursor need not the auxiliary of various tensio-active agents or template, prepares pattern rule, size homogeneous, clean cut, disperses SnO preferably through the method for simple to operation and environmental protection
2Three-dimensional hollow ball rarely has report.
Summary of the invention
The technical problem that the present invention will solve is the deficiency that overcomes above-mentioned technology; Provide a kind of operate simple and easy, pollution-free, cost is low, the single step hydrothermal method of good product dispersibility; Through regulation and control reaction system Central Plains material usage, temperature of reaction and extraneous factors such as time, stirring and ultrasound condition, prepared the SnO that a kind of high adsorption capacity, crystal particle diameter are little, have three-dimensional structure
2The hollow ball nano material.
A kind of SnO with three-dimensional structure
2Hollow ball material is characterized in that, the three-dimensional hollow structure of this material is by unidimensional SnO
2The directed gathering of nanometer rod self-assembly forms, and its mean diameter is 190nm, the about 50nm of outer wall thickness, and crystal particle diameter is about 12nm.
Technical scheme of the present invention is following:
(1) SnO
2The preparation of precursor solution: 0.8～3.00ml concentrated hydrochloric acid is dropwise joined stirring simultaneously in 0.12～0.48g glass putty, add 30～90ml absolute ethyl alcohol then, obtain white solution;
(2) hydro-thermal reaction: the white solution that makes in the above-mentioned steps (1) is transferred in the reaction kettle, and the sealing back is reacted 6～12h down in 180～200 ℃;
(3) washing: with the product in the above-mentioned steps (2) through repeated water washing, alcohol wash, the high speed centrifugation after drying, obtain having the SnO of three-dimensional hollow ball pattern
2White powder.
Agitation condition among the present invention is the room temperature～50 ℃ following 0.5～2.5h of stirring.
Among the present invention, can the white solution that make in the above-mentioned steps (1) be carried out supersound process before shifting, supersound process is no more than 0.5h for ultrasonic frequency 100Hz handles down.
Drying conditions among the present invention is 40～80 ℃ of drying 6～12h.The invention has the beneficial effects as follows:
(1) preparation technology of the present invention is simple to operation, both can be used for experimental implementation, can satisfy suitability for industrialized production again, need not special or expensive device.
(2) SnO of the present invention's preparation
2Three-dimensional hollow ball good in integrity, size homogeneous, pattern rule, good dispersivity.
(3) SnO of the present invention's preparation
2Three-dimensional hollow ball quality is high, is prone to repetition, and required cost is low.
(4) do not use poisonous and hazardous organic solvent among the present invention, do not add any tensio-active agent, starting material are cheap and easy to get, are a kind of environmentally friendly preparing methods.
Description of drawings
Fig. 1 a is the SnO of preparation
2The field emission scanning electron microscope figure (FESEM) of three-dimensional hollow ball, magnification is 100,000 times.
Fig. 1 b is the SnO of preparation
2The field emission scanning electron microscope figure (FESEM) of three-dimensional hollow ball, magnification is 200,000 times.
Fig. 1 c is the SnO of preparation
2The field emission scanning electron microscope figure (FESEM) of three-dimensional hollow ball, magnification is 200,000 times.
Fig. 2 is the SnO of preparation
2The transmission electron microscope picture (TEM) of three-dimensional hollow ball, magnification is 500,000 times.
Fig. 3 is the SnO of preparation
2The x-ray diffraction pattern (XRD) of three-dimensional hollow ball.X-coordinate is twice diffraction angle (2 θ), and ordinate zou is diffraction peak intensity (cps).
Embodiment
Be described in detail embodiment of the present invention below in conjunction with technical scheme.
Embodiment 1
This instance provides a kind of SnO
2Three-dimensional hollow ball preparation of nanomaterials, specific as follows:
In the 0.12g glass putty, dropwise add the 0.8ml concentrated hydrochloric acid; Add the 30ml absolute ethyl alcohol under the room temperature behind the vigorous stirring 2h again; Then the white solution that obtains is transferred in the 50ml reaction kettle, sealing is placed under 200 ℃, takes out reaction kettle room temperature naturally cooling behind the hydro-thermal reaction 10h.Product in the reaction kettle is washed, after high speed centrifugation separates, placed 80 ℃ to obtain SnO behind the dry 6h down through repeated water washing, alcohol
2Three-dimensional hollow ball.
Embodiment 2
This instance provides a kind of SnO
2Three-dimensional hollow ball preparation of nanomaterials, specific as follows:
In the 0.16g glass putty, dropwise add the 1.0ml concentrated hydrochloric acid; Add the 30ml absolute ethyl alcohol under the room temperature behind the vigorous stirring 0.5h again; Obtain white solution; To pass through the above-mentioned solution of 100Hz supersound process 0.5h then and transfer in the 50ml reaction kettle, the reaction kettle sealing will be placed under 200 ℃, take out reaction kettle room temperature naturally cooling behind the hydro-thermal reaction 12h.Product in the reaction kettle is washed, after high speed centrifugation separates, placed 60 ℃ to obtain SnO behind the dry 8h down through repeated water washing, alcohol
2Three-dimensional hollow ball.
Embodiment 3
This instance provides a kind of SnO
2Three-dimensional hollow ball preparation of nanomaterials, specific as follows:
In the 0.36g glass putty, dropwise add the 2.0ml concentrated hydrochloric acid; Add the 60ml absolute ethyl alcohol again behind 30 ℃ of following vigorous stirring 1.5h of water bath with thermostatic control; Obtain white solution; To pass through the above-mentioned solution of 100Hz supersound process 0.2h then and transfer in the 100ml reaction kettle, the reaction kettle sealing will be placed under 180 ℃, take out reaction kettle room temperature naturally cooling behind the hydro-thermal reaction 14h.Product in the reaction kettle is washed, after high speed centrifugation separates, placed 70 ℃ to obtain SnO behind the dry 8h down through repeated water washing, alcohol
2Three-dimensional hollow ball.
Embodiment 4
This instance provides a kind of SnO
2Three-dimensional hollow ball preparation of nanomaterials, specific as follows:
In the 0.48g glass putty, dropwise add the 3.0ml concentrated hydrochloric acid; Add the 90ml absolute ethyl alcohol under the room temperature behind the vigorous stirring 2.5h again; Obtain white solution; To pass through the above-mentioned solution of 100Hz supersound process 0.2h then and transfer in the 100ml reaction kettle, the reaction kettle sealing will be placed under 200 ℃, take out reaction kettle room temperature naturally cooling behind the hydro-thermal reaction 9h.Product in the reaction kettle is washed, after high speed centrifugation separates, placed 80 ℃ to obtain SnO behind the dry 10h down through repeated water washing, alcohol
2Three-dimensional hollow ball.
Embodiment 5
SnO to the present invention's preparation
2Three-dimensional hollow ball nano material carries out pattern and crystalline structure characterizes, and is specific as follows:
(1) morphology analysis
With field emission scanning electron microscope (FESEM) and the technological SnO of transmission electron microscope (TEM) to the present invention's preparation
2Three-dimensional hollow ball carries out pattern, size and surface physics structural analysis, sees Fig. 1 a, Fig. 1 b, Fig. 1 c and Fig. 2.By finding out SnO among Fig. 1 a and Fig. 1 b
2Three-dimensional hollow ball is evenly distributed, regular shape, and surface irregularity, mean diameter is 190nm.Can find out the hollow structure of product significantly by the ball of top end opening among Fig. 1 c, the outer wall that also can observe hollow ball simultaneously is by one dimension SnO
2The nanometer rod gathering forms, and thickness is about 50nm.
Can find out the SnO of the present invention's preparation by Fig. 2 transmission electron microscope picture
2Three-dimensional hollow ball clean cut, surperficial indentation; Simultaneously also can more clearly observe SnO
2Nanometer rod becomes hollow ball as basic construction unit aggregately stacked, has further proved the three-dimensional structure of product.And by SnO among the TEM
2Bright centre portions and the contrast between the black border of ball can be judged, and this material has hollow structure.
(2) X-ray diffracting spectrum (XRD) is analyzed
With the SnO of X-ray diffraction technology to preparing by the present invention
2The crystalline structure of three-dimensional hollow ball is analyzed.Curve among Fig. 3 is respectively the SnO of the present invention's preparation
2Three-dimensional hollow ball and SnO
2Standard card figure (JCPDs No.41-41145).After contrasting analysis, can know the SnO of the present invention's preparation with standard card
2Three-dimensional hollow ball is a tetragonal spheroidal rutile phase.The diffraction peak that does not occur other material in the spectrogram is explained the SnO that the present invention prepares
2Has higher purity.By following Scherrer formula:
D＝Kλ/βcosθ
Can extrapolate SnO by the present invention's preparation
2The median size of three-dimensional hollow ball nano material is 12.38nm.
D is the thickness along the crystal face vertical direction in the formula, also can think the size of crystal grain; K is a diffraction peak shape constant, generally gets 0.89; λ is the wavelength of X-ray, and the present invention gets λ=0.15418nm; β is the peak width at half of diffraction peak; θ is a Bragg angle.
Claims (5)
1. SnO
2Three-dimensional hollow ball preparation of nanomaterials is characterized in that comprising the steps:
(1) SnO
2The preparation of precursor solution:, 0.8～3.00ml concentrated hydrochloric acid is dropwise joined stirring simultaneously in 0.12～0.48g glass putty, add 30～90ml absolute ethyl alcohol then, obtain white solution;
(2) hydro-thermal reaction: the white solution that makes in the above-mentioned steps (1) is transferred in the reaction kettle, reacted 6～12h down in 180～200 ℃;
(3) washing: the product in the above-mentioned steps (2) is washed after drying through centrifugal, washing, alcohol, obtain having the SnO of three-dimensional hollow ball pattern
2White powder.
2. according to claims 1 described a kind of SnO
2Three-dimensional hollow ball preparation of nanomaterials is characterized in that: the stirring in the step (1) is carried out under room temperature～50 ℃, stirs duration 0.5～2.5h.
3. according to claims 1 or 2 described a kind of SnO
2Three-dimensional hollow ball preparation of nanomaterials is characterized in that: the white solution that makes in the above-mentioned steps (1) was carried out supersound process before shifting, ultrasonic frequency 100Hz handles down and is no more than 0.5h.
4. according to claims 1 or 2 described a kind of SnO
2Three-dimensional hollow ball preparation of nanomaterials, it is characterized in that: the drying conditions in the step (3) is 40～80 ℃ of drying 6～12h.
5. according to claims 3 described a kind of SnO
2Three-dimensional hollow ball preparation of nanomaterials, it is characterized in that: the drying conditions in the step (3) is 40～80 ℃ of drying 6～12h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104118904A (en) * | 2014-07-01 | 2014-10-29 | 济南大学 | Preparation method and application of three-dimensional hollow multilevel-structured stannic oxide gas-sensitive material |
| CN104176768A (en) * | 2013-05-22 | 2014-12-03 | 北京化工大学 | Metal-doped tin oxide transparent dispersion and preparation method |
| CN105259211A (en) * | 2015-10-13 | 2016-01-20 | 武汉工程大学 | Gas-sensor nanometer sensitive material, slurry with gas-sensor nanometer sensitive material, preparing method of gas-sensor nanometer sensitive material, preparing method of slurry and application of gas-sensor nanometer sensitive material |
| CN105271374A (en) * | 2015-11-21 | 2016-01-27 | 河南师范大学 | Preparation method of stannic oxide microspheres of oriented connection microstructure |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101638247A (en) * | 2009-08-26 | 2010-02-03 | 福州大学 | Method for preparing tin dioxide nano hollow sphere comprising nano rods and application in lithium battery |
| 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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2012
- 2012-04-20 CN CN2012101193604A patent/CN102627316A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101638247A (en) * | 2009-08-26 | 2010-02-03 | 福州大学 | Method for preparing tin dioxide nano hollow sphere comprising nano rods and application in lithium battery |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| LIFEN XIAO ET AL.: "One-pot template-free synthesis, formation mechanism, and lithium ions storage property of hollow SnO2 microspheres", 《JOURNAL OF SOLID STATE ELECTROCHEMISTRY 》, vol. 14, no. 6, 27 June 2009 (2009-06-27), pages 931 - 936 * |
| XIONGWEN LOU ET AL.: "Template-free synthesis of SnO2 hollow nanostructures with high lithium storage capacity", 《ADVANCED MATERIALS》, vol. 18, no. 17, 28 August 2006 (2006-08-28), pages 2325 - 2329 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104176768A (en) * | 2013-05-22 | 2014-12-03 | 北京化工大学 | Metal-doped tin oxide transparent dispersion and preparation method |
| CN104176768B (en) * | 2013-05-22 | 2016-04-20 | 北京化工大学 | A kind of metal-doped tin oxide transparent dispersion and preparation method thereof |
| CN104118904A (en) * | 2014-07-01 | 2014-10-29 | 济南大学 | Preparation method and application of three-dimensional hollow multilevel-structured stannic oxide gas-sensitive material |
| CN104118904B (en) * | 2014-07-01 | 2016-03-02 | 济南大学 | The preparation method of three-dimensional hollow multilevel hierarchy stannic oxide gas sensitive and application thereof |
| CN105259211A (en) * | 2015-10-13 | 2016-01-20 | 武汉工程大学 | Gas-sensor nanometer sensitive material, slurry with gas-sensor nanometer sensitive material, preparing method of gas-sensor nanometer sensitive material, preparing method of slurry and application of gas-sensor nanometer sensitive material |
| CN105271374A (en) * | 2015-11-21 | 2016-01-27 | 河南师范大学 | Preparation method of stannic oxide microspheres of oriented connection microstructure |
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Application publication date: 20120808 |