CN100577572C - Method for preparing Zn-doped SnO2 micropore nanophase materials - Google Patents
Method for preparing Zn-doped SnO2 micropore nanophase materials Download PDFInfo
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- CN100577572C CN100577572C CN200810114570A CN200810114570A CN100577572C CN 100577572 C CN100577572 C CN 100577572C CN 200810114570 A CN200810114570 A CN 200810114570A CN 200810114570 A CN200810114570 A CN 200810114570A CN 100577572 C CN100577572 C CN 100577572C
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Abstract
The invention belongs to the chemical technical field, and provides a method for preparing a Zn-intermingled with SnO2 micro-pore nanometer material. The method comprises the steps of (a) blending uniformly 6-16 parts by weight of quadrivalence pink salt, 1-3 parts by weight of Zinc salt, 20-40 parts by weight of hexadecyl trimethyl ammonium bromide, 100-200 parts by weight of neovaricaine, and 500-600 parts by weight of distilled water; (b) placing a solution obtained through the step (a) into a high pressure-resistant teflon container; closing the container hemitically; heating with microwave to 160 to 200 DEG C; and reacting for 10-15 minutes; (c) washing a product obtained through the step (b); centrifuging; drying and obtaining the Zn-intermingled with SnO2 micro-pore nanometer material. The surface of the Zn-intermingled with SnO2 micro-pore nanometer material obtained through the method can reach 120m<2>/g, and the pore size thereof is 1.1nm. The method has the characteristics of short reaction time and easy large-scale industrialized production.
Description
Technical field
The invention belongs to chemical technology field, particularly relate to a kind of Zn-doping SnO
2The preparation method of micropore nanophase materials.
Background technology
SnO
2Be a kind of very important broad-band gap n-N-type semiconductorN material (electronic band gap is 3.6 electron-volts), have important use to be worth in fields such as the high performance opto-electronic device of preparation, gas sensor, transparent semiconductor electrode, catalyzer.Discovering of recent years worked as SnO
2The size of particle is reduced to nanometer (10
-9Rice) during range scale, its many physics, chemical property change thereupon.Such as, nano SnO
2The gas sensitization degree of particle can increase by 100 times with respect to its macroscopic material form, improved the detection sensitivity that it detects various hazardous gases such as inflammable, explosive greatly.Why this qualitative change can take place, be since when the volume of particle by macroscopical form (more than the micro-meter scale) when becoming nanoscale, its surface-area has increased widely.The increase of surface-area makes it can touch gas molecule how to be measured, thereby causes its gas sensitization degree to improve greatly.Therefore, synthetic SnO
2Nano material has become a research focus in world today's chemistry, material field, and all can have many about SnO every year on international academic journals
2The report of nano material synthetic method.
SnO commonly used
2The nano material synthetic method is a physical evaporation method, generally needs the Heating temperature more than 1000 degrees centigrade, and is very high to the requirement of equipment, is unfavorable for suitability for industrialized production.
The solution that latest developments have gone out some cryogenic (100-200 degrees centigrade) is combined to method, as hydrothermal method, sol-gel method, solvent-thermal method or the like.By these solution phase methods, can synthesize the SnO of highly crystalline
2Nano material.But these present methods exist a common shortcoming: generated time is long.At present, the use hydrothermal method of reporting in the various documents, solvent-thermal method, the synthetic SnO of sol-gel method
2The generated time of nano material is 15 hours to 3-5 days.This is because the type of heating that these methods adopted is thermal conduction, and this mode heat transfer efficiency is lower, thereby needs the long reacting by heating time.Improved SnO this long heat-up time greatly
2The cost of nano material suitability for industrialized production is unfavorable for large-scale industrial production.
Summary of the invention
In view of above problem, main purpose of the present invention is to provide a kind of Zn-doping SnO
2The preparation method of micropore nanophase materials, this kind method adopts the mode of microwave heating, has the advantages that the reaction times is short, be easy to large-scale industrial production.
This kind Zn-doping SnO provided by the invention
2The preparation method of micropore nanophase materials may further comprise the steps:
A. at first the raw material of following weight ratio is mixed:
Tetravalence pink salt 6～16;
Zinc salt 1～3;
Cetyl trimethylammonium bromide 20～40;
Thanomin 100～200;
Distilled water 500～600;
B. above-mentioned steps gained solution is packed in the container of high pressure resistant Teflon, reacted 10-15 minute airtight, microwave heating to 160～200 ℃ again;
C. with the above-mentioned steps products therefrom through water and washing with alcohol, centrifugation then, drying promptly obtain Zn-doping SnO
2Micropore nanophase materials.
The Zn-doping SnO that adopts present method to obtain
2Micropore nanophase materials has very large surface-area, has reached 120m
2/ g, pore size are about 1.1 nanometers.
Wherein, the tetravalence pink salt is optional with tin chloride, nitric acid tin, tin sulphate etc. among the described step a;
Zinc salt can be selected zinc chloride, zinc nitrate, zinc acetate etc. for use among the described step a;
Cetyl trimethylammonium bromide is as tensio-active agent among the described step a, and thanomin is as coordination agent, and distilled water is as solvent;
Raw material reagent is all analytical pure among the described step a;
The raw material mixing step of described step a is preferably: the tetravalence pink salt with parts by weight 6～16 mixes with the zinc salt of parts by weight 1～3 earlier, the cetyl trimethylammonium bromide that adds parts by weight 20～40 then, the thanomin that adds parts by weight 100～200 again adds the distilled water of parts by weight 500～600 at last;
The gained mixing solutions preferably adopts magnetic agitation to become the liquid of clear, colorless among the described step a;
The prepared Zn-doping of described step c SnO
2Micropore nanophase materials, it has the ethanol susceptibility of height to measure demonstration by air-sensitive character.
Studies show that microwave is a kind of good heating source, because its radiating thermaltransmission mode, its heating rate is very high, can make temperature rise to hundreds of degree centigrade and homogeneous heating from room temperature in the time in several seconds.By adding certain cetyl trimethylammonium bromide tensio-active agent, under more than 100 degrees centigrade condition, synthesized among the present invention by SnO as the crystalline structure growth directed agents
2The microvoid structure that nanoparticle assembles.
More specifically, adopt cetyl trimethylammonium bromide (CTAB) as tensio-active agent among the present invention, it can form micella in the aqueous solution, the micellar shape can be controlled by regulating its concentration, under higher concentration, cetyl trimethylammonium bromide can form three-dimensional micella, wherein Sn
4+Can be adsorbed on above this three-dimensional micella, form Sn
4+-CTAB skeleton.When beginning microwave heating, Sn
4+Hydrolysis forms SnO
2, like this, just formed SnO
2-CTAB skeleton structure, and at last with ethanol with the CTAB wash-out, promptly formed SnO
2Microvoid structure.
In sum, this kind Zn-doping SnO provided by the invention
2The preparation method of micropore nanophase materials adopts microwave heating, has the following advantages:
1) speed of response is very fast, and entire reaction only needs 10-15 minute
Microwave can be transmitted to reaction soln inside makes dipole molecule with high hunting of frequency, cause the effects such as electromagnetic oscillation of molecule, increase the motion of molecule, cause the generation of heat, so microwave heating is a kind of omnibearing heating means, reaction system is whole to be among the spread scope of microwave, from top to bottom, from the inside to surface, heating improves speed of reaction greatly everywhere;
2) thermal inertia is little
Microwave is instantaneous heat temperature raising to dielectric material, and energy consumption is very low, and on the other hand, the output rating of microwave is adjustable at any time, but there is not the residual activity phenomenon in the change thereupon of medium temperature rise inertialess, the needs that be highly advantageous to control automatically and serialization are produced;
3) efficient energy-saving
Generate heat owing to the material that contains moisture very easily directly absorbs microwave,, therefore except that a spot of transmission loss, almost do not have other losses, than the about 30%-50% of general conventional heating power saving not through other intermediate conversion links;
4) be easy to large-scale industrial production
Because reacting by heating is short, the cost of suitability for industrialized production is low, is easy to large-scale industrial production.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is further specified, but the qualification of the present invention of not opposing:
Embodiment 1
By weight 6: 2: 20: take by weighing tin tetrachloride, zinc chloride, cetyl trimethylammonium bromide, thanomin, distilled water at 100: 500, mix after magnetic agitation becomes colourless transparent solution, then this solution is transferred in the container of Teflon, airtight, microwave heating to 160 ℃ reaction 10 minutes, product after water and washing with alcohol, centrifugation, drying, product is characterized by the Zn-doping SnO of highly crystalline through powder x-ray diffraction (XRD), transmission electron microscope (TEM)
2Poromerics, it has the ethanol susceptibility of height to measure demonstration through air-sensitive character.
Embodiment 2
By weight 10: 3: 40: take by weighing tin sulphate (IV), zinc acetate, cetyl trimethylammonium bromide, thanomin, distilled water at 200: 600, mix after magnetic agitation becomes colourless transparent solution, then this solution is transferred in the container of Teflon, airtight, microwave heating to 200 ℃ reaction 15 minutes, product after water and washing with alcohol, centrifugation, drying, product is characterized by the Zn-doping SnO of highly crystalline through powder x-ray diffraction (XRD), transmission electron microscope (TEM)
2Poromerics, it has the ethanol susceptibility of height to measure demonstration through air-sensitive character.
Embodiment 3
By weight 15: 3: 30: take by weighing nitric acid tin (IV), zinc chloride, cetyl trimethylammonium bromide, thanomin, distilled water at 150: 600, mix after magnetic agitation becomes colourless transparent solution, then this solution is transferred in the container of Teflon, airtight, microwave heating to 180 ℃ reaction 15 minutes, product after water and washing with alcohol, centrifugation, drying, product is characterized by the Zn-doping SnO of highly crystalline through powder x-ray diffraction (XRD), transmission electron microscope (TEM)
2Poromerics, it has the ethanol susceptibility of height to measure demonstration through air-sensitive character.
Below its summary of the invention has been done to elaborate.For persons skilled in the art, any conspicuous change of under the prerequisite that does not deviate from the principle of the invention it being done can not exceed the protection domain of the application's claims.
Claims (6)
1, a kind of Zn-doping SnO
2The preparation method of micropore nanophase materials is characterized in that, may further comprise the steps:
A. at first the raw material of following weight ratio is mixed:
Tetravalence pink salt 6～16;
Zinc salt 1～3;
Cetyl trimethylammonium bromide 20～40;
Thanomin 100～200;
Distilled water 500～600;
B. above-mentioned steps gained solution is packed in the container of high pressure resistant Teflon, reacted 10-15 minute airtight, microwave heating to 160～200 ℃ again;
C. with the above-mentioned steps products therefrom through water and washing with alcohol, centrifugation then, drying promptly obtain Zn-doping SnO
2Micropore nanophase materials.
2, a kind of Zn-doping SnO according to claim 1
2The preparation method of micropore nanophase materials is characterized in that, the tetravalence pink salt preferably adopts tin chloride, nitric acid tin or tin sulphate among the described step a.
3, a kind of Zn-doping SnO according to claim 1
2The preparation method of micropore nanophase materials is characterized in that, zinc salt preferably adopts zinc chloride, zinc nitrate, zinc acetate among the described step a.
4, a kind of Zn-doping SnO according to claim 1
2The preparation method of micropore nanophase materials is characterized in that, raw material reagent is all analytical pure among the described step a.
5, a kind of Zn-doping SnO according to claim 1
2The preparation method of micropore nanophase materials is characterized in that, the raw material mixing step of described step a is preferably: the tetravalence pink salt with parts by weight 6～16 mixes with the zinc salt of parts by weight 1～3 earlier; The cetyl trimethylammonium bromide that adds parts by weight 20～40 then; The thanomin that adds parts by weight 100～200 again; The distilled water that adds parts by weight 500～600 at last.
6, a kind of Zn-doping SnO according to claim 1
2The preparation method of micropore nanophase materials is characterized in that, the gained mixing solutions preferably adopts magnetic agitation to become the liquid of clear, colorless among the described step a.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885471B (en) * | 2010-07-27 | 2012-11-07 | 武汉理工大学 | Hydrothermal synthesis method of zinc-doped tin oxide with hollow cubic structure |
| CN102060520A (en) * | 2010-11-01 | 2011-05-18 | 郑州大学 | Method for preparing zinc oxide composite material |
| CN102212796B (en) * | 2011-05-18 | 2013-06-12 | 浙江大学 | Non-magnetic ions Zn<2+>, Mg<2+> and Al<3+> doped SnO2-based magnetic semiconductor film material and preparation method thereof |
| CN103101967A (en) * | 2011-11-14 | 2013-05-15 | 南开大学 | Preparation method three-dimensional multistage SnO2 nanoflowers |
| PL231314B1 (en) * | 2012-11-07 | 2019-02-28 | Univ Jagiellonski | Oxide catalyst carrier for low temperature combustion of methane from sources of low-calorie and its manufacturing |
| CN108545770B (en) * | 2018-07-02 | 2020-06-16 | 河北镭传科技有限责任公司 | Surface-modified Pd-SnO2Preparation method and application of microspheres |
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Non-Patent Citations (2)
| Title |
|---|
| Properties of nanocrystalline SnO2 obtained by means of amicrowave process. A. Cirera et al.Materials Science and Engineering C,Vol.15 . 2001 |
| Properties of nanocrystalline SnO2 obtained by means of amicrowave process. A. Cirera et al.Materials Science and Engineering C,Vol.15 . 2001 * |
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