CN102602986A - Preparation method of micronano stannic oxide porous rod with controllable shape - Google Patents
Preparation method of micronano stannic oxide porous rod with controllable shape Download PDFInfo
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- CN102602986A CN102602986A CN2012101087395A CN201210108739A CN102602986A CN 102602986 A CN102602986 A CN 102602986A CN 2012101087395 A CN2012101087395 A CN 2012101087395A CN 201210108739 A CN201210108739 A CN 201210108739A CN 102602986 A CN102602986 A CN 102602986A
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- tindioxide
- oxalic acid
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Abstract
The invention discloses a preparation method of a micronano stannic oxide porous rod with controllable shape. The method comprises the following steps: dissolving the raw material (soluble tin salt) and oxalate in a certain proportion in the mixed solvent of ethylene glycol and water, stirring and reacting at the room temperature in the presence of polyethylene glycol as an additive, collecting the precipitate to obtain rod-like stannous oxalate precursor, and then calcining at a certain temperature to obtain the micronano stannic oxide porous rod. The preparation method disclosed by the invention has low requirements on equipment and technique, is unlikely to introduce other impurities and is lower in cost. In comparison with other methods, the preparation method is simpler and easier in control of the production structure, and is easy for large-scale production.
Description
Technical field
The present invention relates to the preparation method of the controlled micro-nano tindioxide porous rod of a kind of pattern, belong to the nano material preparation technical field.
Background technology
Tindioxide (SnO
2) be a kind of important wide energy level n-N-type semiconductorN MOX, energy gap is about 3.6eV, has very high transsmissivity and lower resistivity at visible region.Therefore tindioxide has excellent photoelectric and air-sensitive performance, makes it have widespread use in fields such as luminescent material, light absorbing material, catalyzer, gas sensor, transmitter, lithium ion battery negative materials.In addition, tindioxide also has following characteristic: the physics of material, chemicalstability are good, and erosion resistance is strong; To gas detection is reversible, and absorption, desorption time weak point can use continuously for a long time; Safety is higher, satisfactory mechanical property; Resistance generally is the para-curve variation tendency with concentration change; Though the energy gap broad obtains suitable electrical characteristic easily.Tindioxide receives much concern as a kind of new and high technology material at present, and its specific performance properties of the pattern of tindioxide and size impact is one of the focus in investigation of materials field so how to prepare the nano-stannic oxide of ad hoc structure.
As a kind of very important semiconductor material, SnO
2Pattern and size nano semiconductor material character such as luminous, conduction, catalysis, electrochemical activity etc. are had material impact, so nanostructure SnO
2Controlledly synthesis seem extremely important, this also is SnO
2The gordian technique of nano-device Application Areas.And as the bar-shaped SnO of one dimension porous
2Nano material; Because of its special one dimension Nano structure; As microstructure have perforation pore as much as possible, more smooth pore surface, than bigger serface, less low wet electric resistance etc.; Demonstrate the character such as light, electricity, magnetic, heat, suction ripple of a series of excellences, have broad application prospects in following nanometer field.Over past ten years, people utilize the whole bag of tricks to synthesize multiple one dimension SnO again successively
2Nano material like nanotube, nanometer rod, nano wire, nano belt and nano-wire array etc., makes one dimension SnO
2The design of nano structural material and the synthetic new research focus in nanometer material science field that becomes rapidly.
At present, the method for preparing tindioxide mainly comprises solid phase method, liquid phase method and vapor phase process etc., and in liquid phase method, common have the precipitator method, hydrothermal method, microemulsion method and a sol-gel method etc.Li Yadong (Mater.Lett., 1999,1,23-26) adopt ydrogen peroxide 50 method through putty powder under the condition that sulfuric acid exists to prepare tin oxide nano particles, but this method corrodibility is big, is unfavorable for large-scale production; Hou Dedong (J.Inorg.Mater., 2002,17,691-695) prepared nanometer tin dioxide rod, but this method need consume a large amount of raw materials and contaminate environment through the microemulsion template; Xue Xinyu (J.Phys.Chem.C., 2010,114,3968-3972) utilize the synthetic homogeneous of microemulsion template and hydrothermal method to carry the platinum nanometer tin dioxide rod, but this method desired raw material is relatively more expensive and same contaminate environment.Compare with aforesaid method, utilizing the presoma pyrogenic silica to prepare tindioxide porous nano rod has the advantage of self, can control the structure of presoma easily through liquid-phase precipitation, and one-step calcination can obtain the pure preferably phase title product of crystallinity then.This process operation is simple, and not too harsh to equipment, technical requirements, environmental pollution is little, be difficult for introducing other impurity, and raw materials cost is low, and the structure of regulation and control product is comparatively convenient, is a kind of easy, material preparation method of being prone to row.
Summary of the invention
To the deficiency of prior art, it is a kind of reasonable in design that the present invention provides, and technology is simple, the preparation method of the micro-nano tindioxide porous rod that pattern is controlled.
Technical scheme of the present invention is to have designed a kind of simple presoma pyrogenic silica, and as solvent, solubility pink salt and oxalic acid are raw material with the mixed solution of terepthaloyl moietie and zero(ppm) water, and polyoxyethylene glycol is as additive, at first synthetic bar-shaped SnC
2O
4Presoma obtains the bar-shaped tindioxide of micro-nano porous through calcination processing then.
The preparation method of the micro-nano tindioxide porous rod that pattern according to the invention is controlled, step is:
(1) be that 1: 9～9: 1 mixed is as solvent by volume with terepthaloyl moietie and zero(ppm) water; Restrain with 0.1～8 by polyoxyethylene glycol and solvent: the proportional of 30mL adds polyoxyethylene glycol in solvent; Put and stir 10～30 minutes on the magnetic stirring apparatus, make polyoxyethylene glycol dissolve fully, subsequent use;
(2) solubility pink salt and oxalic acid are added respectively in the solution that step (1) makes, on magnetic stirring apparatus, stirred 10-30 minute, it is dissolved fully, obtain tin-salt solution and oxalic acid solution;
(3) be that oxalic acid solution that 1: 5～1: 60 ratio makes step (2) adds in the tin-salt solution that step (2) makes in pink salt and oxalic acid mol ratio; Stir; Room temperature kept after 1～5 hour, and with 1000～4000 rev/mins of condition spinnings, throw out is used deionized water and washing with alcohol respectively 3～5 times with post reaction mixture; Put in 100 ± 10 ℃ the baking oven dryly then, obtain white bar-shaped SnC
2O
4Presoma;
(4) SnC that step (3) is obtained
2O
4Presoma was calcined 1～6 hour in 400～700 ℃ of retort furnaces, made micro-nano tindioxide porous rod.
Among the preparation method of the micro-nano tindioxide porous rod that above-mentioned pattern is controlled, said terepthaloyl moietie of step (1) and zero(ppm) water preferably are 1: 5～5: 1 mixed by volume.
Among the preparation method of the micro-nano tindioxide porous rod that above-mentioned pattern is controlled, said polyoxyethylene glycol of step (1) and solvent are preferably with 0.1～4 gram: the proportional of 30mL adds polyoxyethylene glycol in solvent.
Among the preparation method of the micro-nano tindioxide porous rod that above-mentioned pattern is controlled, the preferred tin protochloride of the said solubility pink salt of step (2).
Among the preparation method of the micro-nano tindioxide porous rod that above-mentioned pattern is controlled, the mol ratio of said pink salt of step (3) and oxalic acid is preferably 1: 20～and 1: 50.
Among the preparation method of the micro-nano tindioxide porous rod that above-mentioned pattern is controlled, preferred 2～4 hours of said room temperature hold-time of step (3).
Among the preparation method of the micro-nano tindioxide porous rod that above-mentioned pattern is controlled, the said calcining temperature of step (4) is preferably 450～600 ℃.
Among the preparation method of the micro-nano tindioxide porous rod that above-mentioned pattern is controlled, the said calcination time of step (4) is preferably 2.5～4.5 hours.
With present compared with techniques, among the preparation method of the micro-nano tindioxide porous rod that pattern according to the invention is controlled, adopt the presoma pyrogenic silica, react simple and easy to control; The products therefrom thing is mutually simple, the SnO of preparation
2Be size adjustable micro-nano porous rod structure.Through the amount of polyoxyethylene glycol that control adds, the size of adjustable micro-nano porous rod and pattern.Because it has bigger serface and high surface, and special crystalline structure, surface property and characterization of adsorption, thereby can be widely used in semi-conductor, solar cell, gas sensor and the optical technology.
Existing tindioxide one-dimensional nano structure material preparation method and route more or less exist the process complicacy, use expensive reagent, and toxicity is bigger, the uneven first-class problem of size.The invention provides a kind of presoma pyrogenic silica preparation method of rutile phase micro-nano tindioxide porous rod, this method technology is simple, and the tindioxide porous rod controllable size of gained is evenly distributed.
Description of drawings
Fig. 1 XRD figure, wherein: the SnC that a is prepared
2O
4The XRD figure of presoma; The SnO that b is prepared
2XRD figure.
Fig. 2 SnO
2The TEM picture of porous rod.
Embodiment
Embodiment 1:
(1) measure 5mL terepthaloyl moietie and 25mL zero(ppm) water mixes in the 100mL beaker, add 0.1 gram polyoxyethylene glycol, put on the magnetic stirring apparatus and stirred 20 minutes, make polyoxyethylene glycol dissolve fully, subsequent use;
(2) tin protochloride and oxalic acid are added respectively in the solution that step (1) makes, on magnetic stirring apparatus, stirred 10 minutes, it is dissolved fully, obtain stannous chloride solution and oxalic acid solution;
(3) be that oxalic acid solution that 1: 20 ratio makes step (2) adds in the stannous chloride solution that step (2) makes in tin protochloride and oxalic acid mol ratio; Stir; Room temperature kept after 2 hours, and with 2000 rev/mins of condition spinnings, throw out is used deionized water and washing with alcohol respectively 3 times with the mixture behind the beaker internal reaction; Put in 100 ℃ the baking oven dryly then, obtain white bar-shaped SnC
2O
4Presoma;
(4) SnC that step (3) is obtained
2O
4Presoma was calcined 3 hours in 500 ℃ of retort furnaces, made micro-nano tindioxide porous rod.
Embodiment 2:
(1) measure 10mL terepthaloyl moietie and 20mL zero(ppm) water mixes in the 100mL beaker, add 3 gram polyoxyethylene glycol, put on the magnetic stirring apparatus and stirred 20 minutes, make polyoxyethylene glycol dissolve fully, subsequent use;
(2) tin protochloride and oxalic acid are added respectively in the solution that step (1) makes, on magnetic stirring apparatus, stirred 20 minutes, it is dissolved fully, obtain stannous chloride solution and oxalic acid solution;
(3) be that oxalic acid solution that 1: 25 ratio makes step (2) adds in the stannous chloride solution that step (2) makes in tin protochloride and oxalic acid mol ratio; Stir; Room temperature kept after 3 hours, and with 3000 rev/mins of condition spinnings, throw out is used deionized water and washing with alcohol respectively 4 times with the mixture behind the beaker internal reaction; Put in 100 ℃ the baking oven dryly then, obtain white bar-shaped SnC
2O
4Presoma;
(4) SnC that step (3) is obtained
2O
4Presoma was calcined 3 hours in 450 ℃ of retort furnaces, made micro-nano tindioxide porous rod.
Embodiment 3:
(1) measure 25mL terepthaloyl moietie and 5mL zero(ppm) water mixes in the 100mL beaker, add 4 gram polyoxyethylene glycol, put on the magnetic stirring apparatus and stirred 20 minutes, make polyoxyethylene glycol dissolve fully, subsequent use;
(2) tin protochloride and oxalic acid are added respectively in the solution that step (1) makes, on magnetic stirring apparatus, stirred 30 minutes, it is dissolved fully, obtain stannous chloride solution and oxalic acid solution;
(3) be that oxalic acid solution that 1: 40 ratio makes step (2) adds in the stannous chloride solution that step (2) makes in tin protochloride and oxalic acid mol ratio; Stir; Room temperature kept after 3 hours, and with 1000 rev/mins of condition spinnings, throw out is used deionized water and washing with alcohol respectively 5 times with the mixture behind the beaker internal reaction; Put in 100 ℃ the baking oven dryly then, obtain white bar-shaped SnC
2O
4Presoma;
(4) SnC that step (3) is obtained
2O
4Presoma was calcined 3.5 hours in 600 ℃ of retort furnaces, made micro-nano tindioxide porous rod.
Claims (8)
1. the preparation method of the controlled micro-nano tindioxide porous rod of a pattern, step is:
(1) be that 1: 9～9: 1 mixed is as solvent by volume with terepthaloyl moietie and zero(ppm) water; Restrain with 0.1～8 by polyoxyethylene glycol and solvent: the proportional of 30mL adds polyoxyethylene glycol in solvent; Put and stir 10～30 minutes on the magnetic stirring apparatus, make polyoxyethylene glycol dissolve fully, subsequent use;
(2) solubility pink salt and oxalic acid are added respectively in the solution that step (1) makes, on magnetic stirring apparatus, stirred 10～30 minutes, it is dissolved fully, obtain tin-salt solution and oxalic acid solution;
(3) be that oxalic acid solution that 1: 5～1: 60 ratio makes step (2) adds in the tin-salt solution that step (2) makes in pink salt and oxalic acid mol ratio; Stir; Room temperature kept after 1～5 hour, and with 1000～4000 rev/mins of condition spinnings, throw out is used deionized water and washing with alcohol respectively 3～5 times with post reaction mixture; Put in 100 ± 10 ℃ the baking oven dryly then, obtain white bar-shaped SnC
2O
4Presoma;
(4) SnC that step (3) is obtained
2O
4Presoma was calcined 1～6 hour in 400～700 ℃ of retort furnaces, made micro-nano tindioxide porous rod.
2. the preparation method of the controlled micro-nano tindioxide porous rod of pattern according to claim 1 is characterized in that said terepthaloyl moietie of step (1) and zero(ppm) water are 1: 5～5: 1 mixed by volume.
3. the preparation method of the controlled micro-nano tindioxide porous rod of pattern according to claim 1 is characterized in that, said polyoxyethylene glycol of step (1) and solvent are with 0.1～4 gram: the proportional of 30mL adds polyoxyethylene glycol in solvent.
4. the preparation method of the controlled micro-nano tindioxide porous rod of pattern according to claim 1 is characterized in that the said solubility pink salt of step (2) is a tin protochloride.
5. the preparation method of the controlled micro-nano tindioxide porous rod of pattern according to claim 1 is characterized in that the mol ratio of said pink salt of step (3) and oxalic acid is 1: 20～1: 50.
6. the preparation method of the controlled micro-nano tindioxide porous rod of pattern according to claim 1 is characterized in that the said room temperature hold-time of step (3) is 2～4 hours.
7. the preparation method of the controlled micro-nano tindioxide porous rod of pattern according to claim 1 is characterized in that the said calcining temperature of step (4) is 450～600 ℃.
8. the preparation method of the controlled micro-nano tindioxide porous rod of pattern according to claim 1 is characterized in that the said calcination time of step (4) is 2.5～4.5 hours.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102774879A (en) * | 2012-08-24 | 2012-11-14 | 云南大学 | Preparation method of dual-phase coexistence one-dimensional structure tin dioxide |
| CN105734481A (en) * | 2014-12-10 | 2016-07-06 | 辽宁法库陶瓷工程技术研究中心 | Preparation method of high-temperature-resistant nano wave absorbing agent and wave absorbing coating |
| CN105948106A (en) * | 2016-06-29 | 2016-09-21 | 渤海大学 | Preparation method of narrow-bandgap stannic oxide semiconductor nanomaterial |
| CN106966426A (en) * | 2017-04-21 | 2017-07-21 | 常州市好利莱光电科技有限公司 | A kind of preparation method of nanoporous stannous oxide |
| CN110467217A (en) * | 2019-08-29 | 2019-11-19 | 西安工程大学 | A kind of preparation method of coralloid nano tin dioxide powder |
| CN112479272A (en) * | 2020-12-01 | 2021-03-12 | 苏州麦茂思传感技术有限公司 | Porous NiO/SnO2Preparation method of nano composite gas-sensitive material |
| CN113008946A (en) * | 2021-03-03 | 2021-06-22 | 南开大学 | Ag-doped SnO2Preparation method of gas-sensitive material |
| CN114082978A (en) * | 2021-11-29 | 2022-02-25 | 大连大学 | Nano AgSn-SnO2Preparation method of needle-shaped composite powder |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101046459A (en) * | 2007-04-26 | 2007-10-03 | 华东师范大学 | Multilayer nanometer porous SnO2 film and its synthesis process |
| CN101323463A (en) * | 2007-06-12 | 2008-12-17 | 赣州瑞德化工有限公司 | Production process of high pure superfine tin oxide |
| CN102080261A (en) * | 2010-12-15 | 2011-06-01 | 哈尔滨师范大学 | Method for synthesizing porous SnO2 nano-wire harness |
-
2012
- 2012-04-13 CN CN2012101087395A patent/CN102602986A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101046459A (en) * | 2007-04-26 | 2007-10-03 | 华东师范大学 | Multilayer nanometer porous SnO2 film and its synthesis process |
| CN101323463A (en) * | 2007-06-12 | 2008-12-17 | 赣州瑞德化工有限公司 | Production process of high pure superfine tin oxide |
| CN102080261A (en) * | 2010-12-15 | 2011-06-01 | 哈尔滨师范大学 | Method for synthesizing porous SnO2 nano-wire harness |
Non-Patent Citations (1)
| Title |
|---|
| YUTAO HAN ET AL.: "Porous SnO2 nanowire bundles for photocatalyst and Li ion battery applications", 《CRYSTENGCOMM》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102774879A (en) * | 2012-08-24 | 2012-11-14 | 云南大学 | Preparation method of dual-phase coexistence one-dimensional structure tin dioxide |
| CN105734481A (en) * | 2014-12-10 | 2016-07-06 | 辽宁法库陶瓷工程技术研究中心 | Preparation method of high-temperature-resistant nano wave absorbing agent and wave absorbing coating |
| CN105734481B (en) * | 2014-12-10 | 2018-02-27 | 辽宁法库陶瓷工程技术研究中心 | A kind of preparation method of high-temperature resistant nano wave absorbing agent and microwave absorbing coating |
| CN105948106A (en) * | 2016-06-29 | 2016-09-21 | 渤海大学 | Preparation method of narrow-bandgap stannic oxide semiconductor nanomaterial |
| CN106966426A (en) * | 2017-04-21 | 2017-07-21 | 常州市好利莱光电科技有限公司 | A kind of preparation method of nanoporous stannous oxide |
| CN106966426B (en) * | 2017-04-21 | 2018-11-16 | 浙江百传网络科技有限公司 | A kind of preparation method of nanoporous stannous oxide |
| CN110467217A (en) * | 2019-08-29 | 2019-11-19 | 西安工程大学 | A kind of preparation method of coralloid nano tin dioxide powder |
| CN110467217B (en) * | 2019-08-29 | 2021-12-28 | 西安工程大学 | Preparation method of coralline nano tin dioxide powder |
| CN112479272A (en) * | 2020-12-01 | 2021-03-12 | 苏州麦茂思传感技术有限公司 | Porous NiO/SnO2Preparation method of nano composite gas-sensitive material |
| CN113008946A (en) * | 2021-03-03 | 2021-06-22 | 南开大学 | Ag-doped SnO2Preparation method of gas-sensitive material |
| CN114082978A (en) * | 2021-11-29 | 2022-02-25 | 大连大学 | Nano AgSn-SnO2Preparation method of needle-shaped composite powder |
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Application publication date: 20120725 |