CN101863511B - Method for preparing monoclinic phase vanadium dioxide and doped nano powder thereof - Google Patents
Method for preparing monoclinic phase vanadium dioxide and doped nano powder thereof Download PDFInfo
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- CN101863511B CN101863511B CN 201010219865 CN201010219865A CN101863511B CN 101863511 B CN101863511 B CN 101863511B CN 201010219865 CN201010219865 CN 201010219865 CN 201010219865 A CN201010219865 A CN 201010219865A CN 101863511 B CN101863511 B CN 101863511B
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Abstract
The invention provides a method for preparing nano powder of monoclinic phase vanadium dioxide by using a hydrothermal-high temperature solid phase synthesis method. The method comprises the following steps of: a) reacting a vanadium source with a reducing agent to obtain vanadium dioxide (VO2)(B), VO2(A) or VO2 (paramontroseite) by using a hydrothermal method; b) washing the VO2(B), the VO2(A) or the VO2 (paramontroseite) and then thoroughly drying the VO2(B), the VO2(A) or the VO2 (paramontroseite) to form powder; c) vacuum-packaging the powder of the VO2(B), the VO2(A) or the VO2 (paramontroseite) in an airtight and high-temperature resistant container; and d) annealing the container at the temperature of between 350 and 1,200 DEG C for over 3 hours to obtain the nano powder of the monoclinic phase vanadium dioxide. The method has the characteristics of simple production technology, low production cost, environmental friendliness, higher product yield, higher product purity and easy industrial mass production.
Description
Technical field
The present invention relates to the nano material synthesis technical field, especially relate to employing hydro-thermal-high temperature solid phase synthesis and prepare VO
2(M) method of nano-powder.
Background technology
Vanadium (V) oxygen compound is that a class is generally acknowledged important thermochromic material.Along with the variation of envrionment temperature, the crystalline structure of oxyvanadium compound, domain structure, magnetic structure can change a lot, thereby cause the huge change on its optical characteristics.In the middle of various oxyvanadium compounds, monoclinic phase VO
2(M) be subject to the extensive concern of scientific circles and industry member due to suitable transformation temperature always, namely in the time of 68 ℃, monoclinic phase VO
2(M) (cryogenic insulation phase) can be transformed into cubic Rutile Type VO
2(R) (hot metal phase), specific conductivity can occur 10 simultaneously
5The transformation of the order of magnitude, infrared transmission performance also can change into from infrared light transmission infrared light tight.This special property makes VO
2(M) in opto-electronic conversion, solar energy intelligent window aspect has inestimable using value.If particularly pass through at VO
2(M) mix the elements such as appropriate tungsten (W), molybdenum (Mo), titanium (Ti) in, its transformation temperature can be reduced to room temperature (20--30 ℃) by 68 ℃, but the characteristic that still keeps its infrared regulation and control, this has just widened its using value more, particularly in the practical application of building energy saving field.
Up to the present, the preparation method who has a hypovanadic oxide powder of Intelligent infrared performance of control mainly contains three kinds: a kind of is vapour deposition VO under logical hydrogen or inert atmosphere protection
2(M) or the pyrolytic decomposition suitable precursors, but this method requirement condition is harsh, and equipment is complicated, not only needs expensive equipment and material cost to be difficult to control simultaneously the valence state of vanadium wherein, seldom arrives a large amount of VO
2(M) pure phase powder or film.Another kind method is to use V by under high temperature
2O
5And V
2O
3Quantitative reaction prepares, and is too high but this temperature of reaction requires, and generally all at 700-800 degree centigrade, the reaction metering is restive, and product is very impure.Also having a kind of method is that some soluble compound that will contain V is dissolved in ethanol, then burning preparation VO
2(M), but the vanadium source of this method demand is more special, and the combustion method industrial operation is dangerous, easily produces a large amount of dust, and needs to consume a large amount of solvents, and cost is very high, and the purity of product neither be high especially.This makes has intelligence every the monoclinic phase VO of infrared control
2(M) preparation cost of nano-powder improves greatly, and is difficult to obtain pure VO
2(M) nano-powder is difficult for accomplishing scale production.
To sum up, VO
2(M) defective of the prior art of preparation field is that preparation condition is harsh, the equipment complex and expensive, and production cost is high, and product yield and purity are low, and environment is unfriendly, is unsuitable for industrialized production etc.
Summary of the invention
The object of the present invention is to provide a kind of monoclinic phase VO
2The production technique that nano-powder preparation method, the method have is simple, production cost is low, environmental friendliness, product yield and purity is higher, the characteristics of easy industrial mass production method.
According to one of purpose of the present invention, a kind of method for preparing the monoclinic phase vanadium dioxide nano powder is provided, it comprises the steps: a) to utilize hydrothermal method, with vanadium source and reductive agent reaction, obtains VO
2(B), VO
2(A) or VO
2(paramontroseite); B) with described VO
2(B), VO
2(A) or VO
2(paramontroseite) after the washing, thorough oven dry is Powdered; C) with described VO
2(B), VO
2(A) or VO
2(paramontroseite) powder Vacuum Package is in airtight, high-temperature resistant container; And d) described container is annealed more than 3 hours in the scope of 350～1200 ℃ ℃, obtain the monoclinic phase vanadium dioxide nano powder.
Mechanism of the present invention is: VO
2(M) (being monoclinic phase vanadium dioxide), VO
2(B) (being the B phase hypovanadic oxide), VO
2(A) (being the A phase hypovanadic oxide) and VO
2(paramontroseite) (being the paramontroseite phase hypovanadic oxide) belongs to isomers.Under the reaction conditions that adopts known hydrothermal method or solvent thermal, as raw material, under the reductive agent effect, be very easy to a large amount of synthetic VO with the vanadium source
2(B), VO
2(A) or VO
2(paramontroseite), however will be VO
2(B) (perhaps VO
2(A) and VO
2(paramontroseite)) Quantitative yield is VO fully
2(M), must be through the high-temperature annealing process of 500 degrees centigrade.Due at VO
2(B), VO
2(A), VO
2(paramontroseite) and VO
2(M) in, vanadium is all positive tetravalence, the valence state that mediates, and this makes the extremely difficult control of annealing process, to very difficult accurately omnidistance control of the atmosphere of reactant.If in annealing atmosphere if any the O of trace
2, can be mixed with V in product
6O
13, or V
2O
5Deng impurity; And if annealing is at an inert atmosphere (N
2Perhaps Ar) in or under the environment of a complete anoxic, again can be because of VO under high temperature
2(B), VO
2(A), VO
2(paramontroseite) in, oxygen is escaped, and can be mixed with V again in product
5O
9, or V
2O
3Deng impurity.The present invention is the pure VO with complete drying
2(B), VO
2(A) or VO
2(paramontroseite) be encapsulated in airtight a, high-temperature resistant container, and give vacuum environment, can make VO like this
2(B), VO
2(A), VO
2(paramontroseite) the fully quantitative VO that is converted in high-temperature annealing process
2(M), avoided the generation of impurity.
Method provided by the present invention, the time of its annealing can not be too short, if too short VO
2(B), VO
2(A), VO
2(paramontroseite) can not be converted into VO fully
2(M), easy residual minim raw material impurity, especially when producing in enormous quantities, calcination time generally all should be more than 3h.Theoretically, the time is longer, and product is purer.
According to an embodiment of the invention, vanadium source described in a step comprises VO (acac)
2, V
2O
5, NH
4VO
3, Na
3VO
4, VOSO
4Perhaps their arbitrary composition.
According to another embodiment of the present invention, described in a step, reductive agent comprises H
2C
2O
4, formic acid, thioacetamide, methyl alcohol, phenylcarbinol or their arbitrary composition.
According to an embodiment more of the present invention, the washings that washing step described in the b step adopts is distilled water or industrial alcohol or dehydrated alcohol.The temperature of baking step described in the b step is 60～150 ℃.
VO
2(B), VO
2(A), VO
2(paramontroseite) etc. need complete washes clean and oven dry before encapsulation, can avoid like this impurity to enter among last finished product, and can be conducive to Vacuum Package.
One of according to the embodiment of the present invention, airtight described in the c step, high-temperature resistant container is airtight Glass tubing, airtight silica tube, airtight alumina crucible, airtight zirconium white crucible or airtight high-melting-point inert metal crucible.Described VO
2(B), VO
2(A) or VO
2(paramontroseite) powder and described airtight, volume ratio high-temperature resistant container are 1: 1～1: 1000.
For the preparation of pure vanadium dioxide, the temperature of high temperature annealing is generally in 500 about degree, and the softening temperature of simple glass is 600 degrees centigrade of left and right, so for the preparation of sterling vanadium dioxide, adopt the simple glass pipe to get final product.If prepare other adulterated powders, annealing temperature may correspondingly improve, can Choice of Quartz Tube Diameters, alumina crucible, zirconium white crucible or other high-melting-point inert metal crucible, and be used for synthesis reaction temperature and reach the material of thousands of degrees centigrade.Volume airtight, high-temperature resistant container can not be excessive can not be too small, need to do accommodation according to the volume of middle powder, if volume of a container is excessive, easily generate V
3O
4, V
2O
3, V
3O
5, V
5O
9Deng impurity; Too small, be unfavorable for Vacuum Package.
According to the present invention, when needs prepare the monoclinic phase vanadium dioxide nano-powder of doping, soluble tungsten source, molybdenum source, titanium source or chromium source are added described vanadium source to become the powder of doping in step a, then sequentially react, will obtain the monoclinic phase vanadium dioxide nano powder of corresponding doping in steps d.
One of according to the embodiment of the present invention, above-mentioned soluble tungsten source, molybdenum source, titanium source or chromium source are 0: 1～0.2: 1 with the ratio of the amount of substance in vanadium source.Soluble tungsten source, molybdenum source, titanium source or chromium source comprise Na
2WO
4, Na
2MoO
4, K
2TiO (C
2O
4)
2, K
2Cr
2O
7, ammonium tungstate, white tungstic acid, (NH
4)
2Mo
2O
7, tetrabutyl titanate, (NH
4)
2CrO
4Perhaps their arbitrary composition.
A kind of hydro-thermal provided by the invention-vacuum annealing method is to utilize the high temperature annealing method of hydro-thermal presoma in the vacuum sealing system to prepare in a large number monoclinic phase VO
2(M) preparation method of hypovanadic oxide powder, the method have the raw material cheapness, cost is low, production unit is ripe simply, the simple characteristics of technology controlling and process.Utilize method provided by the present invention, the yield of product can reach 100%, and phase is pure, if do not add adulterate body in hydro-thermal reaction, finally can obtain not containing the pure VO of any dephasign
2And the size of product has the dimensional effect of general nanoparticle at Nano grade, the monoclinic phase VO that synthesizes (M),
2(M) nano-powder has very superior Intelligent infrared control, is suitable for further using in daily life from now on and industrial production.In addition, the present invention also has the realization of industrialization of being easy to, is easy to produce in enormous quantities and advantages of environment protection.
The present invention is a kind of VO that extensive preparation has the metal insulator phase transformation that is applicable to
2(M) method of nano-powder utilizes hydrothermal method to prepare the isomers VO of the thermodynamics metastable phase of target product
2(B), VO
2(A) and VO
2(paramontroseite).The mediate thermodynamics metastable phase isomers of compound of valence state of utilization obtains the target product of thermodynamically stable phase after Vacuum Package annealing, be applicable to have the preparation of any compound of similar thermodynamic behaviour.Present method adopts suitable precursors, under hot conditions simple preparation the advantage of compound of mediate valence state or lower valency can be generalized to other systems, especially to the high temperature Quantitative yield aspect of isomers have pervasive may.
The aspect that the present invention adds and advantage part in the following description provide, and part will become obviously from the following description, or recognize by practice of the present invention.
Description of drawings
Above-mentioned and/or additional aspect of the present invention and advantage will become from the following description of the accompanying drawings of embodiments and obviously and easily understand, wherein:
Fig. 1 is the schema of method provided by the present invention;
Fig. 2 adopts VO according to one of embodiment of the present invention
2(B) obtain VO
2(M) XRD figure;
Fig. 3 adopts VO according to one of embodiment of the present invention
2(B) obtain VO
2(M) DSC figure;
Fig. 4 adopts VO according to one of embodiment of the present invention
2(A) obtain VO
2(M) XRD figure;
Fig. 5 adopts VO according to one of embodiment of the present invention
2(A) obtain VO
2(M) DSC figure;
Fig. 6 adopts VO according to one of embodiment of the present invention
2(A) obtain VO
2(M) SEM figure;
Fig. 7 adopts VO according to one of embodiment of the present invention
2(B) doping Mo obtains mixing the VO of Mo
2(M) XRD figure;
Fig. 8 adopts VO according to one of embodiment of the present invention
2(B) doping Mo obtains mixing the VO of Mo
2(M) DSC figure;
Fig. 9 adopts VO according to one of embodiment of the present invention
2(B) doping W obtains mixing the VO of W
2(M) XRD figure;
Figure 10 adopts VO according to one of embodiment of the present invention
2(B) doping W obtains mixing the VO of W
2(M) DSC figure;
Figure 11 adopts VO according to one of embodiment of the present invention
2(B) doping W obtains mixing the VO of W
2(M) SEM figure.
Embodiment
The below describes embodiments of the invention in detail, and the example of described embodiment is shown in the drawings.Be exemplary below by the embodiment that is described with reference to the drawings, only be used for explaining the present invention, and can not be interpreted as limitation of the present invention.
The cardinal principle process flow sheet of method provided by the present invention is seen accompanying drawing 1.As shown in the figure, the vanadium source is inserted in reaction vessel.The vanadium source can be adopted well known in the prior art, as VO (acac)
2, V
2O
5, NH
4VO
3, Na
3VO
4, VOSO
4, the perhaps mixture of the arbitrary proportion of above-mentioned substance.Add reductive agent, for example can adopt H
2C
2O
4, formic acid, thioacetamide, methyl alcohol, phenylcarbinol, perhaps above-mentioned two or more are mixed according to actual needs and use.Vanadium source in reaction vessel and reductive agent adopt this area hydrothermal method commonly used to react, and reaction conditions will be adjusted according to the preparation needs, and these concrete conditions can be with reference to prior art.According to the difference of hydrothermal method reaction conditions and reductive agent selection, reaction can obtain VO
2(B) or VO
2(A) or VO
2(paramontroseite).Otherwise, also can determine according to the kind of the intermediate of wishing to get the condition of hydro-thermal reaction.
Then, be with the VO that obtains in the previous step reaction
2(B) or VO
2(A) or VO
2(paramontroseite) wash, drying and processing.Washing composition adopts distilled water or industrial alcohol or dehydrated alcohol usually, and each washs 3 to 5 times, can substantially remove gained VO
2(B) or VO
2(A) or VO
2(paramontroseite) impurity in, the purity of raising finished product.Oven dry can be adopted the method for crucible heating or baking oven for heating, also can adopt other methods commonly used in the art, and the temperature of oven dry is generally 60～150 ℃.Obtain pulverous VO after oven dry
2(B) or VO
2(A) or VO
2(paramontroseite).
Then, in airtight, high-temperature resistant container, vacuum tightness should be tried one's best high with above-mentioned powder Vacuum Package, and this is conducive to improve product purity.Airtight, high-temperature resistant container is to be the simple glass pipe, also can be silica tube, alumina crucible, zirconium white crucible, high-melting-point inert metal crucible, perhaps other any high-temperature resistant containers that meet reaction conditions.In order to improve the purity of reaction efficiency and reaction product, VO
2(B) or VO
2(A) or VO
2(paramontroseite) powder and described airtight, volume ratio high-temperature resistant container be generally 1: 1～and 1: 1000.
At last, the powder in encloses container is carried out annealing reaction, annealing temperature is generally 350～1200 ℃, and the time was generally more than 3 hours.Treat that annealing reaction finishes, after the encloses container naturally cooling, open container, obtain the monoclinic phase vanadium dioxide nano powder, can find out from X-ray powder diffraction collection of illustrative plates (as Fig. 2-11), the purity of the powder that is synthesized is more than 99.99%.
If during the monoclinic phase vanadium dioxide nano-powder of wish preparation doping, before the first step hydro-thermal reaction, soluble tungsten source, molybdenum source, titanium source or chromium source are joined in the vanadium source, then sequentially carry out subsequent reactions, will obtain the monoclinic phase vanadium dioxide nano powder of corresponding doping at end product.The ratio of the amount of substance in the soluble tungsten source of mixing in the vanadium source, molybdenum source, titanium source or chromium source and vanadium source itself is generally 0: 1～and 0.2: 1.Soluble tungsten source, molybdenum source, titanium source or chromium source can be selected from Na
2WO
4, Na
2MoO
4, K
2TiO (C
2O
4)
2, K
2Cr
2O
7, ammonium tungstate, white tungstic acid, (NH
4)
2Mo
2O
7, tetrabutyl titanate, (NH
4)
2CrO
4, the perhaps arbitrary composition of their arbitrary proportions.
Below listed some specific embodiments:
Embodiment 1 uses V0
2(B) as precursor
In being the tetrafluoroethylene reactor of 35ml, volume adds 5mmol V
2O
5And 8mmolH
2C
2O
4, then add 30ml distilled water, after stirring 30min, seal in the metal still shell of packing into, then keep 48h under 200 ℃, after naturally lowering the temperature, centrifugal product, and wash 3 times with distilled water and industrial alcohol, then with sample 60 ℃ of baking 8h in vacuum drying oven, then at 120 ℃ of baking 4h, obtain dry VO
2(B), then with the VO of 1g drying
2(B) vacuum inclosure internal diameter is in the Glass tubing of 8mm, and under 500 ℃, annealing 20h obtains pure VO
2(M).
Its XRD and DSC figure see accompanying drawing 2 and 3, as can be seen from the figure gained XRD peak intensity high especially and also with the standard card spectrogram coincide fine, the DSC peak area is very large, illustrates that the crystallinity of product is fine, purity is also high especially, more than 99.99%.
In being the tetrafluoroethylene reactor of 55ml, volume adds 3mmol VO (acac)
2With 50ml distilled water, after stirring 30min, in the metal still shell of packing into, then keep 24h under 220 ℃, naturally after lowering the temperature, the off-line product, and respectively wash 3 times with distilled water and industrial alcohol, then with sample 60 ℃ of baking 8h in vacuum drying oven, then at 120 ℃ of baking 4h, obtain dry VO
2(A), then with the VO of 200mg drying
2(B) vacuum inclosure internal diameter is in the Glass tubing of 8mm, and under 500 ℃, annealing 20h obtains pure VO
2(M).
Its XRD and DSC figure see attached Figure 4 and 5, as can be seen from the figure the XRD of products therefrom and standard spectrogram coincide fine, illustrate that product is pure VO
2(M).Accompanying drawing 6 is the SEM picture of final product pattern, can find out, products therefrom is the granular powder of hundreds of nanometer.
Embodiment 3 use are mixed the VO of Mo
2(B) as precursor
In being the tetrafluoroethylene reactor of 35ml, volume adds 2.25mmol V
2O
5, 0.25mmolNa
2MoO
4With 4mmol H
2C
2O
42H
2O, then add 30ml distilled water, after stirring 30min, seal in the metal still shell of packing into, then keep 48h under 200 ℃, naturally after the cooling, centrifugal product, and wash 3 times with distilled water and industrial alcohol, then with sample 60 ℃ of baking 8h in vacuum drying oven, at 120 ℃ of baking 4h, obtain the dry VO that mixes Mo again
2(B), then with the VO that mixes Mo of 200mg drying
2(B) to enclose internal diameter be in the Glass tubing of 8mm to vacuum, and under 500 ℃, annealing 20h obtains mixing the VO of Mo
2(M).
Its XRD and DSC figure see accompanying drawing 7 and 8, as can be seen from the figure the XRD of final product and VO
2(M) the standard spectrogram is very identical, and the DSC peak value also is reduced to about 34 ℃, and the extremely successful of doping is described, product purity is also very high.
Embodiment 4 use are mixed the VO of W
2(B) as precursor
In being the tetrafluoroethylene reactor of 35ml, volume adds 2.475mmol V
2O
5, 0.00417mmol ammonium tungstate and 4mmol H
2C
2O
42H
2O, then add 30ml distilled water, after stirring 30min, seal in the metal still shell of packing into, then keep 48h under 200 ℃, naturally after the cooling, centrifugal product, and wash 3 times with distilled water and industrial alcohol, then with sample 60 ℃ of baking 8h in vacuum drying oven, at 120 ℃ of baking 4h, obtain the dry VO that mixes W again
2(B), then with the VO that mixes W of 200mg drying
2(B) to enclose internal diameter be in the Glass tubing of 8mm to vacuum, and under 500 ℃, annealing 20h obtains mixing the VO of W
2(M).
Its XRD and DSC figure see accompanying drawing 9 and 10, as can be seen from the figure the XRD of final product and VO
2(M) the standard spectrogram is very identical, and the DSC peak value also is reduced to about 57.2 ℃, and the extremely successful of doping is described, product purity is also very high.Its shape appearance figure is seen accompanying drawing 11, as can be seen from the figure obtains the powder that doped products is the hundreds of nanometer.
Although illustrated and described embodiments of the invention, for the ordinary skill in the art, be appreciated that without departing from the principles and spirit of the present invention and can carry out multiple variation, modification, replacement and modification to these embodiment, scope of the present invention is limited by claims and equivalent thereof.
Claims (7)
1. method for preparing the monoclinic phase vanadium dioxide nano powder, it comprises the steps:
A) utilize hydrothermal method, with vanadium source and reductive agent reaction, obtain B phase VO
2, A phase VO
2Perhaps paramontroseite phase VO
2
B) with described B phase VO
2, A phase VO
2Perhaps paramontroseite phase VO
2Thoroughly dry after washing and be Powdered;
C) with described B phase VO
2, A phase VO
2Perhaps paramontroseite phase VO
2The powder Vacuum Package in airtight, high-temperature resistant container;
D) described container is annealed more than 3 hours in the scope of 350～1200 ℃, obtain the monoclinic phase vanadium dioxide nano powder;
Wherein, described vanadium source comprises VO(acac)
2, V
2O
5, NH
4VO
3, Na
3VO
4, VOSO
4Perhaps their arbitrary composition; Described reductive agent comprises H
2C
2O
4, formic acid, thioacetamide, methyl alcohol, phenylcarbinol or their arbitrary composition.
2. method as claimed in claim 1, the washings that washing step described in its b step adopts is distilled water or industrial alcohol or dehydrated alcohol.
3. method as claimed in claim 1, described in its b step, the temperature of baking step is 60～150 ℃.
4. method as claimed in claim 1, airtight described in its c step, high-temperature resistant container is airtight Glass tubing, airtight silica tube, airtight alumina crucible, airtight zirconium white crucible or airtight high-melting-point inert metal crucible.
5. method as claimed in claim 1, B phase VO described in its c step
2, A phase VO
2Perhaps paramontroseite phase VO
2Powder and described airtight, volume ratio high-temperature resistant container be 1:1～1:1000.
6. method as claimed in claim 1 wherein when in step a, soluble tungsten source, molybdenum source, titanium source or chromium source being added described vanadium source to become the powder of doping, is reacted, and obtains the monoclinic phase vanadium dioxide nano powder of corresponding doping in steps d.
7. method as claimed in claim 6, wherein said soluble tungsten source, molybdenum source, titanium source or chromium source comprise Na
2WO
4, Na
2MoO
4, K
2TiO (C
2O
4)
2, K
2Cr
2O
7, ammonium tungstate, white tungstic acid, (NH
4)
2Mo
2O
7, tetrabutyl titanate, (NH
4)
2CrO
4Perhaps their arbitrary composition.
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