CN100360423C - Process for synthesizing spinel zine stannate nano rod - Google Patents
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- CN100360423C CN100360423C CNB200610048962XA CN200610048962A CN100360423C CN 100360423 C CN100360423 C CN 100360423C CN B200610048962X A CNB200610048962X A CN B200610048962XA CN 200610048962 A CN200610048962 A CN 200610048962A CN 100360423 C CN100360423 C CN 100360423C
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- spinel
- nano rod
- hydrazine hydrate
- chloride
- zinc
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Abstract
The present invention relates to a method for synthesizing spinel zinc stannate (Zn2SnO4) nanometer rods, which comprises the following steps: using hydrazine hydrate to replace sodium hydroxide or ammonia water as a mineralizing agent; respectively using zinc chloride and stannic chloride as a zinc source and a stannic source; realizing the hydrothermal synthesis of superfine spinel zinc stannate nanometer rods with the diameter of 2 to 5 nm without using the conventional hydrothermal synthesis method which uses sodium hydroxide or ammonia water as a mineralizing agent. The hydrothermal technology proposed by the present invention has the characteristic that hydrazine hydrate, zinc chloride and stannic chloride are utilized to form a coordination compound which is slowly changed into the spinel zinc stannate nanometer rods in a hydrothermal process, and the aim of better controlling the size and the appearance of products is achieved.
Description
Technical field
The present invention relates to a kind of synthetic method of spinel zine stannate nano rod.
Background technology
Because excellent performance and numerous potential are used, the zinc oxide in the binary oxide and the nanostructure of stannic oxide have become the research focus of nanosecond science and technology.Their ternary oxide---spinel zine stannate (Zn
2SnO
4Be called for short ZTO) also be wide bandgap semiconductor (the about 3.6eV of energy gap), because it has very high electronic mobility, high electroconductibility and low visible absorbance, make it all have potential to use in various fields such as solar energy film, inflammable gas detection, wet sensitive device, photochemical catalysis and electronic ceramicss, the nanostructure of ZTO has the nanostructure better properties than zinc oxide and stannic oxide probably, but also is nowhere near about the research of ZTO nanostructure at present.
When the size of nanostructure on certain dimension during less than its exciton Bohr radius, nanostructure might present tangible quantum size effect, and the exciton Bohr radius of most materials is being counted nanometer between 20 nanometers, therefore, prepares the following nanostructure of 5 nanometers and has special meaning.At present, the preparation method of the ZTO nanostructure of open report has: thermal evaporation, mechanical milling method and high temperature solid-state reactions method.Thermal evaporation and high temperature solid-state reactions method all need very high temperature (about 1000 ℃); Mechanical milling method can only obtain random nano particle, and prepares very difficulty of the following nano particle of 5 nanometers.Relatively, wet chemistry method has the characteristics of low, the simple to operate and suitable scale operation of cost, the present invention is based on the method that hydrothermal method has proposed a kind of preparation 2～5 nanometer ZTO nano rod.
It is mineralizer that traditional hydrothermal method adopts sodium hydroxide or ammoniacal liquor, can only obtain the spinel zine stannate (J.Fang et al.Mater.Res.Bull., 36,1391 (2001)) of micron or submicron order, and its process is as follows: the OH that sodium hydroxide or ammoniacal liquor ionization go out
-Ion, OH
-With Zn
2+And Sn
4+Ionic reaction generates Zn (OH)
2And Sn (OH)
4, Zn (OH)
2And Sn (OH)
4Generate the Zn of micron or submicron order by hydro-thermal reaction
2SnO
4Hydrazine hydrate is a kind of chemical feedstocks commonly used, cheap, is that the hydro-thermal building-up process of mineralizer is then different, specific as follows with the hydrazine hydrate: before the hydro-thermal reaction, and hydrazine (ligand) and ZnCl
2And SnCl
4Form coordination compound, this coordination thing deferred reaction under hydrothermal condition generates ZTO, reaches the purpose of fine control product size and pattern.
Summary of the invention
The object of the present invention is to provide a kind of synthetic method of spinel zine stannate nano rod, be to utilize hydrazine hydrate to prepare the spinel zine stannate nano rod of 2～5 nanometers for the hydro-thermal technology of mineralizer, this method has simply, the characteristics of cheap and suitable scale operation.
The step of the technical solution used in the present invention is as follows: with zinc chloride and 2: 1 in molar ratio mixed of tin chloride, mixture is put into deionized water for stirring, adding mole number again is the hydrazine hydrate of 8～12 times of tin chlorides, produce the precipitation of white pulpous state this moment, and promptly hydrazine hydrate and zinc chloride and tin chloride have formed coordination compound; Stir after 10～30 minutes, the above-mentioned aqueous solution for preparing is put into autoclave, compactedness is 80～90%, handles 24 hours in 250～300 ℃ of temperature ranges, then with solution centrifugal, the drying handled well, just obtains the nano rod of spinel zine stannate.
The beneficial effect that the present invention has is: traditional hydrothermal method can only obtain the spinel zine stannate crystal of micron or submicron order.Maximum characteristics of the present invention are to adopt hydrazine hydrate (N
2H
4H
2O) replace sodium hydroxide or ammoniacal liquor, realize the synthetic of 2～5 nanometer ZTO nano rod.Hydrazine (ligand) and ZnCl
2And SnCl
4Form coordination compound, this coordination thing deferred reaction under hydrothermal condition generates ZTO, reaches and controls the crystalline growth well.And the raw material that the present invention adopts all is cheap pharmaceutical chemicals, and whole process need not any complexing agent or tensio-active agent.
Description of drawings
Fig. 1 is the XRD figure spectrum of ZTO nano rod;
Fig. 2 is the transmission electron microscope photo of ZTO nano rod, (a) photo under the low power and electron diffraction; (b) photo of several nano rod; (c) the high resolution photo of single nano rod;
Fig. 3 is that employing sodium hydroxide is the hydro-thermal technology synthetic ZTO crystalline transmission electron microscope photo and the electron diffraction pattern of mineralizer.
Embodiment
Embodiment 1:
With 1.7408 gram zinc chloride (ZnCl
2, 0.0128 mole) and 2.2400 gram tin chloride (SnCl
45H
2O, 0.0064 mole) put into 160 ml deionized water, add 2.5600 gram hydrazine hydrate (N again
2H
4H
2O, 0.0512 mole), stir after 10 minutes, the above-mentioned solution for preparing to be put in the polytetrafluoroethyllining lining of autoclave, the liner volume is 200 milliliters, promptly compactedness is 80%.This solution was handled 24 hours down at 250 ℃, solution centrifugal of handling well and drying, obtained the nano rod of the ZTO of 2～4 nanometers.Fig. 1 is the XRD figure spectrum of the nano rod of ZTO, with Zn
2SnO
4Standard card (JCPDS 74-2184) fit like a glove.Fig. 2 is the transmission electron microscope photo of ZTO nano rod, and as can be seen from Figure 2 the product of gained is the monocrystalline ZTO nano rod of 2～4 nanometers.
Embodiment 2:
With 1.7408 gram zinc chloride (ZnCl
2, 0.0128 mole) and 2.2400 gram tin chloride (SnCl
45H
2O, 0.0064 mole) put into 160 ml deionized water, add 2.5600 gram hydrazine hydrate (N again
2H
4H
2O, 0.0512 mole), stir after 10 minutes, the above-mentioned solution for preparing to be put in the polytetrafluoroethyllining lining of autoclave, the liner volume is 200 milliliters, promptly compactedness is 80%.This solution was handled 24 hours down at 300 ℃, solution centrifugal of handling well and drying, obtained the nano rod of the ZTO of 3～5 nanometers.As seen, hydrothermal temperature raises, and crystal is slightly grown up.But when hydrothermal temperature hanged down 250 ℃, the product crystallization was bad.
Embodiment 3:
With 1.7408 gram zinc chloride (ZnCl
2, 0.0128 mole) and 2.2400 gram tin chloride (SnCl
45H
2O, 0.0064 mole) put into 160 ml deionized water, add 3.8400 gram hydrazine hydrate (N again
2H
4H
2O, 0.0768 mole), stir after 10 minutes, the above-mentioned solution for preparing to be put in the polytetrafluoroethyllining lining of autoclave, the liner volume is 200 milliliters, promptly compactedness is 80%.This solution was handled 24 hours down at 250 ℃, solution centrifugal of handling well and drying, obtained the nano rod of the ZTO of 2～4 nanometers, and the result is consistent with embodiment 1, illustrated that hydrazine hydrate concentration is little to the product influence within the specific limits.
Comparative example:
With 1.7408 gram zinc chloride (ZnCl
2, 0.0128 mole) and 2.2400 gram tin chloride (SnCl
45H
2O, 0.0064 mole) put into 160 ml deionized water, add 2.0480 gram sodium hydroxide (NaOH again, 0.0512 mole), stir after 10 minutes, the above-mentioned solution for preparing put in the polytetrafluoroethyllining lining of autoclave, the liner volume is 200 milliliters, and promptly compactedness is 80%.This solution was handled 24 hours down at 250 ℃, solution centrifugal of handling well and drying, obtained the ZTO crystal of 500 nanometers, and its transmission electron microscope photo is seen Fig. 3.Illustrate that adopting sodium hydroxide is mineralizer, the hydro-thermal of difficult realization ZTO nanostructure is synthetic.
Claims (2)
1, a kind of synthetic method of spinel zine stannate nano rod, it is characterized in that: the step of this method is as follows: with zinc chloride and 2: 1 in molar ratio mixed of tin chloride, mixture is put into deionized water for stirring, adding mole number again is the hydrazine hydrate of 8～12 times of tin chlorides, produce the precipitation of white pulpous state this moment, and promptly hydrazine hydrate and zinc chloride and tin chloride have formed coordination compound; Stir after 10～30 minutes, the above-mentioned aqueous solution for preparing is put into autoclave, compactedness is 80～90%, handles 24 hours in 250～300 ℃ of temperature ranges, then with solution centrifugal, the drying handled well, just obtains the nano rod of spinel zine stannate.
2, the synthetic method of a kind of spinel zine stannate nano rod according to claim 1 is characterized in that: the diameter of described nano rod is 2～5 nanometers.
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|---|---|---|---|
| CNB200610048962XA CN100360423C (en) | 2006-01-09 | 2006-01-09 | Process for synthesizing spinel zine stannate nano rod |
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|---|---|---|---|
| CNB200610048962XA CN100360423C (en) | 2006-01-09 | 2006-01-09 | Process for synthesizing spinel zine stannate nano rod |
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|---|---|
| CN1792812A CN1792812A (en) | 2006-06-28 |
| CN100360423C true CN100360423C (en) | 2008-01-09 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100429151C (en) * | 2006-11-13 | 2008-10-29 | 浙江理工大学 | Lanthanum stannate, europium stannate and its composite stannate nanopowder synthesis method |
| CN100462305C (en) * | 2007-03-02 | 2009-02-18 | 浙江理工大学 | Universal synthesizing method for lanthanide series rare earth stannate nano powder |
| CN101943692B (en) * | 2010-08-11 | 2014-02-26 | 上海师范大学 | Air-sensitive material with high-sensitivity and quick-response, and preparation method and application thereof |
| CN102303901B (en) * | 2011-05-24 | 2013-08-21 | 南京大学 | Preparation method, product and use of micro/nano heretically-structured insert octahedral Zn2SnO4 |
| CN103265065B (en) * | 2013-04-22 | 2014-12-03 | 中山大学 | Preparation method of graded zinc stannate macroporous materials |
| CN104001494B (en) * | 2014-06-16 | 2016-04-13 | 洛阳理工学院 | The synthetic method of the graphite modified nano-zinc stannate of one kind |
| CN104150527B (en) * | 2014-06-24 | 2016-06-22 | 济南大学 | A kind of preparation method of hollow tetrakaidecahedron structural hydroxyl zinc gas sensitive |
| CN104961152A (en) * | 2015-07-07 | 2015-10-07 | 昆明理工大学 | Method for preparing zinc stannate under vacuum condition |
| CN104961153B (en) * | 2015-07-23 | 2017-02-08 | 柳州百韧特先进材料有限公司 | Production method of superfine nano sodium stannate |
| CN105366712A (en) * | 2015-12-07 | 2016-03-02 | 西安建筑科技大学 | Synthetic method of zinc stannate by using sodium stannate as raw material |
| CN106564935B (en) * | 2016-11-09 | 2018-04-13 | 陕西科技大学 | A kind of ZnSn (OH)6Powder and its preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86106681A (en) * | 1986-10-09 | 1987-10-21 | 云南大学 | The making of zinc metastannate (zinc stannate) gas sensor |
| WO1991001273A1 (en) * | 1989-07-21 | 1991-02-07 | Alcan International Limited | Method of making metal stannates |
-
2006
- 2006-01-09 CN CNB200610048962XA patent/CN100360423C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86106681A (en) * | 1986-10-09 | 1987-10-21 | 云南大学 | The making of zinc metastannate (zinc stannate) gas sensor |
| WO1991001273A1 (en) * | 1989-07-21 | 1991-02-07 | Alcan International Limited | Method of making metal stannates |
Non-Patent Citations (2)
| Title |
|---|
| Zn2SnO4气敏材料的水热合成及其掺杂改性. 徐甲强等.传感技术学报，第18卷第4期. 2005 * |
| 贵金属催化剂对锡酸锌气敏特性的影响. 徐甲强等.云南大学学报（自然科学版），第19卷第1期. 1997 * |
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