CN101311367B - Tungsten oxide nano-material and method for preparing same - Google Patents
Tungsten oxide nano-material and method for preparing same Download PDFInfo
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- CN101311367B CN101311367B CN200810103880XA CN200810103880A CN101311367B CN 101311367 B CN101311367 B CN 101311367B CN 200810103880X A CN200810103880X A CN 200810103880XA CN 200810103880 A CN200810103880 A CN 200810103880A CN 101311367 B CN101311367 B CN 101311367B
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Abstract
The invention discloses a tungsten oxide nanowire material with a diameter being 10-80 nanometer and a length being 200 nanometers to 5 microns; a chrysanthemum shaped nanowire is developed on AAO surface; the valency of the tungsten is +6. A triblock copolymer P123, WCl6 and a superior level pure absolute ethyl alcohol are confected into sol, according to a weight ratio of (0.4-0.55): (0.8-1.2):(7-14); under a pressure of -0.08- -0.2MPa, the sol is padded in an AAO template hole, rinsed and dried, and then sintered under an atmosphere of high purity argon of 0.3-0.4 cdm/min and the temperature of 450-550 DEG C for 4-6 hours, thus obtaining the tungsten oxide nanowire. The procedures of the preparation method of the invention are simple; the technical parameter in the process of the preparation is easy to control; the energy consumption in the whole preparation process is very low; the feature of the prepared tungsten oxide nanowire is peculiar; a big specific surface is possessed. Important application significance is possessed in fields like a gas sensor, etc.
Description
Technical field
The present invention relates to a kind of tungsten oxide nano-material and preparation method thereof, belong to the preparing technical field of 1-dimention nano oxide material.
Background technology
Tungsten oxide 99.999 is a kind of n N-type semiconductorN, belongs to typical transition metal oxide.As a kind of functional materials,
In recent years, it is found that the tungsten base oxide is except that as catalysis, electrochromism, battery terminal, solar absorptive material and the stealth material, the character that also has semiconductor functional materials such as temperature-sensitive, pressure-sensitive and air-sensitive, the tungsten oxide nanometer epitaxial just more and more causes people's great attention in the application and the research of aspects such as gas sensor, photochemical catalysis, photoconduction, especially in oxide semiconductor gas sensor Application Areas, the Tungsten oxide 99.999 sill has been considered to detect NO
x, SO
x, NH
3, H
2One of the most promising new oxide gas sensitive such as S.
Compare with traditional tungsten oxide material, tungsten oxide nano has bigger specific surface area, and it all is with a wide range of applications at aspects such as gas sensor, electroluminescent, photoluminescence, conductance electrode and photochemical catalysis.Particularly in oxide semiconductor gas sensor Application Areas, tungsten oxide nano is except having big specific surface area, also have bigger surfactivity and stronger adsorptive power, accelerated the reaction with gas, thereby improved sensitivity greatly and further reduced the working temperature of transmitter.
At present, also there are problems such as complicated process of preparation, energy consumption are big in the technology of preparation tungsten oxide nano.
For example, people (C.S.Rout such as India C.S.Rout, et al.Appl.Phys.A, 85:241～246,2006) it is the WO of 5～15 nanometers that the method that study group adopts the auxiliary hydrothermal method of anodised pellumina (AAO) to combine with atmosphere sintering has prepared diameter
3Nano wire.But, WO in this method
3The synthesis technique of nano wire is very complicated, and energy consumption is big, reaches 200 ℃ as the hydrothermal temperature in early stage is higher, and the hydro-thermal time also reaches 24 hours.People (AndreaPonzoni et al.Applied Physics Letters, 88:203101-1～203101-3,2006) such as Andrea Ponzoni have prepared WO by the evaporation tungsten powder in the time of 1400～1450 ℃
3-XThe nanometer line network structure, to be tens nanometers by diameter constitute to the nano wire of 200nm this nanometer line network structure, but parameters such as necessary strict controlled temperature, pressure, evaporation time in preparation process, and entire reaction carries out and feeds the argon gas of certain flow rate in vacuum chamber, preparation temperature is up to 1400～1450 ℃, this has increased energy consumption to a great extent, is difficult for realizing scale operation.
Summary of the invention
At the problem that exists in the tungsten oxide nano-material preparation process at present, it is a kind of by easy sol-gel processing that one of purpose of the present invention is to provide, the tungsten oxide nano-material that the mass preparation pattern is peculiar.Observe by high resolution field emission scanning electron microscope (FESEM:LEO1530), the diameter of described tungsten oxide nano is 10～80 nanometers, and length is 200 nanometers to 5 micron, and pattern is made of wire and large-sized chrysanthemum shape of mutual winding.Compare with existing tungsten oxide nano, find that after the research of x-ray photoelectron power spectrum the tungsten in the prepared tungsten oxide nano of the present invention is+6 valencys, and this nano wire has peculiar pattern, has bigger specific surface area, combining with the AAO carrier directly to be used as the sensitive membrane of gas sensor, and this has crucial value and realistic meaning in the gas sensor field.
Another object of the present invention is to provide with AAO is the method for the above-mentioned tungsten oxide nano of preparing carriers, can improve the surface-volume ratio of tungsten oxide material simultaneously, can improve various catalysis, opto-electronic device and the air-sensitive performance of Tungsten oxide 99.999 sill.Employed method is very simple, promptly adopts traditional sol-gel processing to combine with the AAO template, does not need the restriction of severe condition such as high temperature, high vacuum, high pressure.This method may further comprise the steps:
(1) with triblock copolymer P123, WCl
6Press (0.4～0.55) with the pure dehydrated alcohol of top grade: (0.8～1.2): the weight ratio of (7～14) is mixed with colloidal sol;
(2) (0.08MPa)～(under pressure 0.2MPa) colloidal sol in (1) is filled in the AAO pattern hole;
(3) will fill template behind the colloidal sol with dehydrated alcohol and deionized water rinsing after vacuum-drying 8～12 hours between 55～65 ℃;
(4) dried template in (3) is being made tungsten oxide nano in sintering between 450～550 ℃ after 4～6 hours under the high-purity argon gas atmosphere.By the X-ray photoelectron spectroscopic analysis result among Fig. 5 as can be seen, the tungsten in our the finally prepd tungsten oxide nano is+6 valencys.
In above-mentioned steps (1), the process for preparation of whole colloidal sol all needs magnetic agitation.
What specify is need under certain negative pressure AAO pattern hole gas inside be discharged before in step (2), so that step (2) can be carried out smoothly.
The thickness of described AAO template is 60 microns, and the nanoporous diameter of AAO template is between 100～200 nanometers.
The flow control of high-purity argon gas is at 0.3～0.4 cubic decimeter/minute in the described step (4).
Advantage of the present invention and positively effect are: preparation method and preparation process are very simple, and the processing parameter in the preparation process is controlled easily, and the energy consumption of whole process of preparation is considerably less, and the tungsten oxide nano pattern of preparation is peculiar, has big specific surface area.
Description of drawings
Fig. 1 is the surface topography synoptic diagram that is used to prepare the AAO template carrier of tungsten oxide nano-material.
Fig. 2 is the EDAX results synoptic diagram of AAO template shown in the square frame among Fig. 1.
Fig. 3 be use emission scan electron microscopic observation to embodiment 1 in the tungsten oxide nano-material synoptic diagram.
Fig. 4 represent use emission scan electron microscopic observation to embodiment 1 in chrysanthemum shape tungsten oxide nano-material synoptic diagram.
Fig. 5 represents the photoelectron spectrum figure of tungsten oxide nano-material among the embodiment 1.
Fig. 6 represent use emission scan electron microscopic observation to embodiment 2 in the tungsten oxide nano-material synoptic diagram.
Embodiment
Further specify the present invention below in conjunction with embodiment.
Embodiment one:
The raw material of the preparation colloidal sol that is adopted in the present embodiment, is that the purity that pure dehydrated alcohol of top grade and ALDRICH produce is the WCl of 99.9+%
6And molecular weight (Mn) is 5800 triblock copolymer P123.
At first, need the anodic oxidation aluminium formwork shown in Fig. 1 (Fig. 2 is the energy spectrogram of this template) be fixed and be sealed in the sand hopper with paraffin, under certain negative pressure AAO pattern hole gas inside is discharged then, purpose is easier the carrying out of filling process that makes colloidal sol.
1, preparation colloidal sol
Accurate a certain amount of P123 of weighing, WCl
6With the pure dehydrated alcohol of top grade, make P123, WCl
6With the weight ratio of the pure dehydrated alcohol of top grade be 0.5: 1: 10, earlier be dissolved in load weighted P123 in the pure dehydrated alcohol of load weighted top grade and carry out magnetic agitation fully until the P123 dissolving, this moment is again with load weighted WCl
6Slowly join above-mentioned the dissolving completely in the P123 solution, carry out magnetic agitation simultaneously until WCl
6Dissolve fully and form flaxen colloidal sol.
2, fill the AAO template
The colloidal sol that just prepared in above-mentioned 1 is filled in the AAO template under the pressure of-0.1Mpa;
3, handle the early stage after the filling AAO template
Use respectively behind dehydrated alcohol and the deionized water rinsing 3 times in vacuum drying oven in 60 ℃ of dryings 10 hours filling template behind the colloidal sol;
4, set sintering temperature curve
Set 5 hours the time chien shih atmosphere furnace chamber be warming up to 500 ℃ of top temperatures from room temperature, and kept 5 hours in this temperature, be cooled to room temperature naturally for 500 ℃ from top temperature then.
5, atmosphere sintering prepares tungsten oxide nano
With dried template in above-mentioned 3 under high-purity argon gas atmosphere in 500 ℃ of heat preservation sinterings 5 hours, reduce to naturally then and take out sample after the room temperature and just make the peculiar tungsten oxide nano of pattern.Be warming up in the process of cooling whole, the flow velocity of high-purity argon gas remains on 0.35 cubic decimeter/minute always.
In the present embodiment, adopting traditional simple and easy sol-gel processing, is that preparing carriers has gone out the peculiar tungsten oxide nano of pattern with the AAO template, and the shape appearance figure of its field emission scanning electron microscope as shown in Figure 3 and Figure 4.Fig. 5 is the analytical results that its x-ray photoelectron can spectrogram, and as can be seen from Figure 5, the tungsten in the present embodiment in the prepared tungsten oxide nano is+6 valencys.
Embodiment two:
A certain amount of P123 of accurate weighing, WCl when 1, preparing colloidal sol
6With the pure dehydrated alcohol of top grade, make P123, WCl
6With the weight ratio of the pure dehydrated alcohol of top grade be 0.55: 1.2: 14;
2, the colloidal sol that just prepared in above-mentioned 1 is filled under the pressure of-0.2Mpa carried out in the AAO template that negative pressure handles;
3, will fill template behind the colloidal sol uses respectively behind dehydrated alcohol and the deionized water rinsing 3 times in vacuum drying oven in 65 ℃ of dryings 8 hours;
4, the highest sintering temperature is 450 ℃, and temperature rise rate is 100 ℃/hour, and the soaking time in the time of 450 ℃ is 6 hours; The flow velocity of high-purity argon gas is 0.3 cubic decimeter/minute, promptly makes described tungsten oxide nano-material, and prepared tungsten oxide nano as shown in Figure 6.
Embodiment three:
In the present embodiment, the step of being implemented is identical with embodiment one, and different is:
A certain amount of P123 of accurate weighing, WCl when 1, preparing colloidal sol
6With the pure dehydrated alcohol of top grade, make P123, WCl
6With the weight ratio of the pure dehydrated alcohol of top grade be 0.4: 0.8: 7;
2, the colloidal sol that just prepared in above-mentioned 1 is filled under the pressure of-0.08Mpa carried out in the AAO template that negative pressure handles;
3, will fill template behind the colloidal sol uses respectively behind dehydrated alcohol and the deionized water rinsing 3 times in vacuum drying oven in 55 ℃ of dryings 12 hours;
4, the highest sintering temperature is 550 ℃, and temperature rise rate is 100 ℃/hour, and the soaking time in the time of 550 ℃ is 4 hours; The flow velocity of high-purity argon gas is 0.4 cubic decimeter/minute, promptly makes described tungsten oxide nano-material.
Embodiment four:
In the present embodiment, the step of being implemented is identical with embodiment one, and different is:
A certain amount of P123 of accurate weighing, WCl when 1, preparing colloidal sol
6With the pure dehydrated alcohol of top grade, make P123, WCl
6With the weight ratio of the pure dehydrated alcohol of top grade be 0.45: 1.1: 12;
2, the colloidal sol that just prepared in above-mentioned 1 is filled under the pressure of-0.15Mpa carried out in the AAO template that negative pressure handles;
3, will fill template behind the colloidal sol uses respectively behind dehydrated alcohol and the deionized water rinsing 3 times in vacuum drying oven in 65 ℃ of dryings 9 hours;
4, the highest sintering temperature is 550 ℃, and temperature rise rate is 100 ℃/hour, and the soaking time in the time of 550 ℃ is 4.5 hours; The flow velocity of high-purity argon gas promptly makes described tungsten oxide nano-material in 0.38 cubic decimeter/minute scope.
Embodiment five:
In the present embodiment, the step of being implemented is identical with embodiment one, and different is:
A certain amount of P123 of accurate weighing, WCl when 1, preparing colloidal sol
6With the pure dehydrated alcohol of top grade, make P123, WCl
6With the weight ratio of the pure dehydrated alcohol of top grade be 0.52: 0.9: 9;
2, the colloidal sol that just prepared in above-mentioned 1 is filled under the pressure of-0.12Mpa carried out in the AAO template that negative pressure handles;
3, the highest sintering temperature is 480 ℃, and temperature rise rate is 100 ℃/hour, and the soaking time in the time of 480 ℃ was at 5.5 hours;
4, the flow velocity of high-purity argon gas is 0.33 cubic decimeter/minute, promptly makes described tungsten oxide nano-material.
From above five embodiment as can be seen, as long as in preparation process, make various parameters, as proportioning, the pressure when filling colloidal sol, the highest sintering temperature, the flow velocity and the soaking time of high-purity argon gas of each admixture remains in certain scope when preparing colloidal sol, the peculiar pattern of prepared tungsten oxide nano shown in will drawings attached.In concrete implementation process, those skilled in the art can both carry out concrete enforcement according to given process parameters range in the treating processess such as the ratio range of each material of preparation colloidal sol and later stage sintering, does not exceed with given above-mentioned three embodiment of the present invention.
More than by five embodiment the present invention is described in detail; those skilled in the art are to be understood that; in the scope that does not exceed spirit of the present invention and essence; certain modification and distortion that the present invention is made; replace the AAO template among the present invention or set different technical parameters such as different temperature, time and argon gas flow velocity such as the anodic oxidation aluminium formwork that adopts different thickness and aperture; still can realize result of the present invention, and not break away from protection scope of the present invention.
Claims (5)
1. the preparation method of a tungsten oxide nano-material is characterized in that, this method may further comprise the steps:
(1) with triblock copolymer P123, WCl
6With the pure dehydrated alcohol of top grade by 0.4～0.55: 0.8～1.2: 7～14 weight ratio is mixed with colloidal sol;
(2)-0.08MPa～-pressure of 0.2MPa under with step (1) in the colloidal sol of preparation be filled in the pellumina pattern hole;
(3) will fill template behind the colloidal sol with dehydrated alcohol and deionized water rinsing after vacuum-drying 8～12 hours between 55～65 ℃;
(4) dried template in the step (3) is being made described tungsten oxide nano in sintering between 450～550 ℃ under the high-purity argon gas atmosphere after 4～6 hours.
2. the preparation method of a kind of tungsten oxide nano-material according to claim 2 is characterized in that, carries out magnetic agitation in the colloidal sol process for preparation.
3. the preparation method of a kind of tungsten oxide nano-material according to claim 2 is characterized in that, described pellumina template is that thickness is 60 microns, and the nanoporous diameter of pellumina template is the pellumina template of 100～200 nanometers.
4. the preparation method of a kind of tungsten oxide nano-material according to claim 2 is characterized in that, the flow of described high-purity argon gas atmosphere high-purity argon gas is 0.3～0.4 cubic decimeter/minute.
5. the preparation method of a kind of tungsten oxide nano-material according to claim 2 is characterized in that, under certain negative pressure pellumina pattern hole gas inside is discharged before in step (2), so that step (2) can be carried out smoothly.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101701928A (en) * | 2009-10-27 | 2010-05-05 | 武汉理工大学 | Gas-sensitive transducer with nano wall structure and preparation method thereof |
| CN103265081B (en) * | 2013-05-27 | 2015-02-04 | 合肥工业大学 | Method for preparing tungsten oxide nano single crystal by sol-gel method |
| CN103570070A (en) * | 2013-11-07 | 2014-02-12 | 东华大学 | Preparation method of self-assembly W18049 nanostructure |
| CN103864460A (en) * | 2014-03-07 | 2014-06-18 | 天津大学 | Preparation method of sequenced tungsten oxide nanowire array structure |
| CN104909409B (en) * | 2015-06-08 | 2016-08-24 | 陕西科技大学 | A kind of one-dimensional euphorbia milii shape WO3the preparation method of crystallite |
| CN106542580A (en) * | 2016-11-03 | 2017-03-29 | 中国检验检疫科学研究院 | A kind of synthetic method for preparing the tungsten oxide nano of gas sensor |
| CN106745277A (en) * | 2017-02-16 | 2017-05-31 | 重庆文理学院 | A kind of tungsten oxide nano and preparation method thereof |
| CN106865997B (en) * | 2017-02-21 | 2019-06-07 | 上海第二工业大学 | A method of growing tungsten oxide film directly on electro-conductive glass |
| CN108017289B (en) * | 2017-11-30 | 2020-10-27 | 西安理工大学 | Preparation method of amorphous tungsten oxide film |
| CN110967887B (en) * | 2018-09-30 | 2022-09-16 | 马亮 | Electrochromic film and preparation method thereof |
| CN109680178B (en) * | 2018-12-05 | 2020-12-01 | 盐城工学院 | Preparation method and application of tungsten-based nanoflower material |
| CN114477293B (en) * | 2022-03-29 | 2023-12-22 | 吉林大学 | One-dimensional dihalide tungsten dioxide material and preparation method thereof |
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| CN1830813A (en) * | 2006-02-15 | 2006-09-13 | 太原理工大学 | Preparation method of nanometer tungsten trioxide crystallite |
| CN1935671A (en) * | 2006-10-19 | 2007-03-28 | 大连理工大学 | Tungsten oxide material with nano band array structure and its preparing method |
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