CN101700909A - Method of preparing intelligent energy-saving vanadium dioxide by hydrothermal method - Google Patents
Method of preparing intelligent energy-saving vanadium dioxide by hydrothermal method Download PDFInfo
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- CN101700909A CN101700909A CN200910238799A CN200910238799A CN101700909A CN 101700909 A CN101700909 A CN 101700909A CN 200910238799 A CN200910238799 A CN 200910238799A CN 200910238799 A CN200910238799 A CN 200910238799A CN 101700909 A CN101700909 A CN 101700909A
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Abstract
The invention relates to a method of preparing vanadium dioxide by hydrothermal method. The method comprises the following steps: adding oxidant, reducing agent or acidity and alkalinity adjusting agent in a hydrothermal kettle containing proper amount of aqueous solution of the source of vanadium, then placing the hydrothermal kettle in a 40-300 DEG C of oven to perform heat preservation for 30 minutes to 5 days, and centrifuging to collect vanadium dioxide after the reaction is completely finished. The preparation method provided by the invention has simple process, low cost and high yield, the mass production can be realized and the purity of the obtained intelligent energy-saving vanadium dioxide nano-powder is high. Vanadium dioxide doped powder can further be obtained by adding proper amount of compound containing tungsten, molybdenum, manganese, chromium or titanium in the aqueous solution of the source of vanadium to realize wider industrial applications. The control of different appearances of vanadium dioxide nano-powder can be realized by controlling the categories of the source of vanadium and the dosage of oxidant, reducing agent or acidity and alkalinity adjusting agent.
Description
Technical field
The present invention relates to the preparation of monocline phase and cubic rutile phase hypovanadic oxide nano-powder, especially relate to method based on its nano-powder of Hydrothermal Preparation and adulterated powder.
Background technology
Oxyvanadium compound is the very important material with intelligent characteristic of a class, and the variation of envrionment temperature can cause crystalline structure, the domain structure of material, the variation of magnetic structure, thereby causes the bigger variation on the optical characteristics.Especially vanadium dioxide (VO
2) be subjected to people especially and pay close attention to especially.
Monocline phase VO
2(VO
2(M)) with cubic rutile VO mutually
2(VO
2(R)) powder can cause it to external world by phase transformation, as sunlight infrared rays part, carries out intelligent control and realizes intelligent power saving.Monocrystalline VO
2The metal-insulator phase transition temperature approximately be 68 ℃.Under this temperature, VO
2Crystalline structure can change to the low temperature monoclinic phase (isolator character) that places an order from cubic phase rutile structure (metalline) under the high temperature, the transformation of crystalline structure is accompanied by the sudden change of light, electrical property.Monocline phase under from the four directions under the high temperature to low temperature, VO
2Infrared transmittivity sharply raise, and the above sudden change of 5 magnitudes takes place in the direct current resistance coefficient.
VO
2The special property of this metal-insulator phase transition make it have potential to use at aspects such as photoelectric conversion material, optical storage, laser radiation and the controls of form sun power.VO
2Be the material that a kind of typical infrared rays to external world carries out perception and regulation and control, monocline phase (low temperature phase) has the function of infrared permeation, and cubic phase (high temperature phase) has the ultrared characteristic of obstruct, can be used for the automatic adjusting of intelligent house temperature.Therefore, the vanadium dioxide material produces the novel intelligent material of response as a kind of environmental change to external world, has extremely wide intelligent power saving application prospect.Along with the further understanding of people to its variable color rule, particularly, will widen its Application Areas and application mode greatly by variable color stability and temperature susceplibility are further improved, produce remarkable social benefit and economic benefit.
Up to the present, the hypovanadic oxide powder (VO that has the intelligent power saving performance
2(M) and VO
2(R) phase) preparation need under the vapor deposition apparatus of logical hydrogen or inert atmosphere, realize without exception.This method needs expensive cost to be difficult to the valence state of control vanadium wherein simultaneously, is difficult to obtain VO
2Pure phase.This makes monocline mutually and cubic rutile phase hypovanadic oxide (VO2 (M) and VO
2(R)) preparation cost of powder improves greatly, is difficult to accomplish scale production.
Summary of the invention
The object of the present invention is to provide the hypovanadic oxide powder (VO of the preparation intelligent power saving performance that a kind of technology is simple, cost is low, productive rate is high, purity is good and can produce in enormous quantities
2(M) and VO
2(R) method phase).
For realizing above-mentioned at least one goal of the invention, the invention provides a kind of method that adopts the Hydrothermal Preparation vanadium dioxide, comprise: in the water heating kettle that an amount of vanadium source aqueous solution is housed, add oxidation, reduction or acid-base modifier, then with described water heating kettle as in 40 ℃-300 ℃ the baking oven insulation 30 minutes--5 days, after reacting completely, centrifugal collection obtains vanadium dioxide.
The hydro-thermal device of using in the aforesaid method can be a common used in industry stainless steel still reaction unit in this area, also can be common hydro-thermal autoclave, the glass reflux, and other can satisfy the device of technical scheme.
The add-on of oxidation, reduction or acid-base modifier should be calculated according to the kind and the amount in vanadium source, and the implication of " in right amount " makes reaction finally obtain vanadium dioxide fully exactly.
According to an aspect of the present invention, described oxidation, reduction or acid-base modifier comprise oxidisability soda acid, reductibility soda acid, non-oxide, reductibility soda acid or have other materials of oxidation, reductibility and their combination.
According to a further aspect in the invention, the above-mentioned method for preparing vanadium dioxide, wherein said vanadium source comprise metavanadic acid ammonia, sodium orthovanadate, Vanadium Pentoxide in FLAKES, potassium metavanadate, vanadium oxytrichloride, vanadium tetrachloride, vanadylic sulfate, methyl ethyl diketone vanadyl title complex, o-vanillin vanadyl title complex, vanadium trichloride, V
2S
5, VS
2, VOOH, V (OH)
2NH
2, V
2O
3, methyl ethyl diketone vanadium complex and their combination.
According to an aspect of the present invention, utilizing present method gained vanadium dioxide can be the nano-powder of different-shape.Adopt the inventive method,, can realize the control of its pattern and size as long as select different needing only to select different oxidation, reduction or acid-base modifier and the combination in vanadium source.Specifically, be selected from metavanadic acid ammonia, sodium orthovanadate, Vanadium Pentoxide in FLAKES, potassium metavanadate, vanadium oxytrichloride, V when described vanadium source
2S
5The time, described oxidation, reduction or acid-base modifier are selected from the reductibility soda acid or have other materials of reductibility and their combination, and collecting the vanadium dioxide that obtains is even overlong nanowire; When described vanadium source is selected from vanadium tetrachloride, vanadylic sulfate, VS
2, when methyl ethyl diketone vanadyl title complex, o-vanillin vanadyl title complex, described oxidation, reduction or acid-base modifier are selected from non-oxide reductibility soda acid, collecting the vanadium dioxide that obtains is ganoid nano belt; When described vanadium source is selected from vanadium trichloride, VOOH, V (OH)
2NH
2, V
2O
3, during the methyl ethyl diketone vanadium complex, described oxidation, reduction or acid-base modifier are selected from the oxidisability soda acid or have other materials of oxidisability and their combination, collecting the vanadium dioxide that obtains is that hexagonal is flower-shaped.During such as an amount of hydrazine hydrate of adding in the metavanadic acid ammonia soln, can realize the control of even overlong nanowire; Be used in when adding an amount of dilute hydrochloric acid in the aqueous solution of methyl ethyl diketone vanadyl title complex, can realize the control of ganoid nano belt; Be used in the VOOH aqueous solution and add an amount of rare nitric acid and be, can realize control that hexagonal is flower-shaped etc.Simultaneously make the vanadium source effectively be dispersed in the solution, at this time homogeneous nucleation can occur, realize the growth of nanostructure by means of acid-base modifier.
Concrete, among the above-mentioned preparation method, the oxidisability soda acid can be selected from rare nitric acid etc.; The reductibility soda acid can be selected from hydrazine hydrate, formic acid, lactic acid etc.; Non-oxide reductibility soda acid can be selected from dilute hydrochloric acid, dilute sulphuric acid, ammoniacal liquor, sodium hydroxide etc.; Material with oxidation-reduction quality can be selected from sodium borohydride, hydrogen peroxide etc.
Further, the concentration of described vanadium source in described solution is more than the 0.001mol/L.
Mechanism of the present invention is: principle of oxidation and reduction, the vanadium source provides enough vanadium to participate in reaction, an amount of oxidation, reduction or acid-base modifier, the valence state of realizing vanadium in the environment of suitable pH value is fixed at quaternary, forms the preparation of the vanadium dioxide nano powder with intelligent power saving performance in the final insulating process at a lower temperature.
Adopt the inventive method to prepare monoclinic phase vanadium dioxide (VO
2And cubic rutile phase hypovanadic oxide (VO (M))
2(R)) powder, the temperature and time of reaction is one of successful key.If carry out at a lower temperature during reaction, what then obtain will be the bad material of degree of crystallinity; And if temperature is too high, may cause the too fast vanadium dioxide that also can not get pure phase of reaction.Reaction times is too short, equally also will cause the appearance of amorphous phase; And if overlong time can make that the pattern of the vanadium dioxide that makes is more assorted.Suitable reaction temperature and time are respectively 40 ℃-300 ℃ and 30 minutes-5 days.
According to an aspect of the present invention, can be mixed with in the compound or the ion of tungstenic, the compound that contains molybdenum or ion, manganiferous compound or ion, the compound that contains chromium or ion, titaniferous compound or the ion one or more and doping adjustable between 0.1%～10% (mol ratio) in the aqueous solution of described vanadium source.The purpose that is mixed with tungsten, molybdenum, manganese and chromium is to change transformation temperature; The purpose of Doped with Titanium is the transmitance that strengthens visible light.The VO that obtains by this step
2Adulterated powder more can be fit to different industrial application.
According to method provided by the present invention, described vanadium dioxide product comprises nanometer product and adulterated powder, and its metal-insulator phase transition temperature is 20 ℃～68 ℃.
According to preparation method of the present invention, can obtain having monocline phase VO
2(VO
2(M)) with cubic rutile VO mutually
2(VO
2(R)) powder and adulterated powder thereof have the following advantages:
1,, thereby can under the situation that does not need main equipment and severe condition, form in the past monocline which obtains VO mutually because the present invention adopts hydro-thermal synthetic method at a lower temperature
2(VO
2(M)) with cubic rutile VO mutually
2(VO
2(R)) nano-powder.With isoplassont synthetic method ratio mutually in the past, have that raw material is cheap and easy to get, cost is lower; Technology is simple, productive rate is high, system is clean and be easy to amplify the advantage of batch process.
2, monocline phase VO
2(VO
2(M)) with cubic rutile VO mutually
2(VO
2(R)) monocline phase VO in the powder body material
2(low temperature phase) has the function of infrared permeation, and cubic phase VO
2(high temperature phase) has the ultrared characteristic of obstruct.Therefore, this material produces the novel intelligent material of response as a kind of environmental change to external world, can intercept ultrared heat effect and regulating and controlling temperature when temperature is high, thereby realizes the energy conservation characteristic application.
3, the powder that utilizes the present invention to be synthesized has very high purity; and has very superior intelligent power saving cycle performance; intelligence transformation temperature zone has been contained from 20 and has been spent to 68 degree; can extensively satisfy the requirement of aspects such as photoelectric conversion material, optical storage, laser radiation and the control of form sun power, be suitable for further using in daily life from now on and the industrial production.
Additional aspect of the present invention 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
Fig. 1 is according to the XRD of one of embodiment of the invention products therefrom (changeing target X-ray powder diffraction) analysis chart;
Fig. 2 is according to the DSC of one of embodiment of the invention products therefrom (intelligent power saving performance test) curve, contains 20 cyclic curves, is used to illustrate suction, the heat release cycle performance of tested object;
Fig. 3 is the even line FE-SEM photo according to one of embodiment of the invention products therefrom;
Fig. 4 is the smooth nano belt FE-SEM photo according to one of embodiment of the invention products therefrom;
Fig. 5 is according to the flower-shaped FE-SEM photo of the hexagonal of one of embodiment of the invention products therefrom.
Embodiment
Describe embodiments of the invention below in detail, the example of described embodiment is shown in the drawings.Below by the embodiment that is described with reference to the drawings is exemplary, only is used to explain the present invention, and can not be interpreted as limitation of the present invention.
Embodiment 1
Monocline phase VO
2(VO
2(M)) the evenly realization of overlong nanowire: in the 50ml polytetrafluoroethylliner liner, add 2mmol metavanadic acid ammonia (NH
4VO
3), and adding 45ml water, the ammoniacal liquor that the back adds 1ml 1mol/L is dissolved in the alkaline aqueous solution metavanadic acid ammonia fully, adds the 1ml hydrazine hydrate then, stirs 10min.Be placed on 200 ℃ the interior insulation of baking oven 30h behind the sealing hydro-thermal autoclave.Behind the naturally cooling, use the product of deionized water, absolute ethanol washing gained respectively, remove possible impurity.As shown in Figure 1, but all X-ray powder diffraction peaks all index be VO
2(M) powder, and do not have other impurity peaks to occur, so embodiment 1 synthetic is highly purified VO
2(M) powder body material.Fig. 2 is the intelligent power saving The performance test results according to embodiment of the invention products therefrom, test pattern is 20 round-robin measured curves, as can be seen from the figure significantly heat absorption and exothermic peak appear respectively in this product near 63 ℃ and 47 ℃, and each cyclic curve changes basically identical, illustrate that this product has extraordinary heat absorption heat release circulation, the therefore VO that obtains according to method provided by the present invention
2(M) powder body material has very superior intelligent power saving cycle performance, can extensively satisfy the application in the industrial production.Fig. 3 is the FE-SEM photo according to embodiment of the invention products therefrom, can see being even overlong nanowire from photo.This programme is applicable to following combination simultaneously: 2mmol ammonium meta-vanadate+45ml water+1ml formic acid or lactic acid; 2mmol sodium orthovanadate or ortho-vanadic acid potassium or V2O3+45ml water+1ml hydrazine hydrate; 2mmol sodium orthovanadate+45ml water+1ml formic acid or lactic acid; 2mmol V2S5+45ml water+1mmol sodium borohydride; 2mmol vanadium oxytrichloride+45ml water+1ml 1mol/L ammoniacal liquor+1mmol sodium borohydride.
Embodiment 2
Nanometer monocline phase VO
2(VO
2(M)) realization of the smooth nano belt of powder body material: in the 50ml polytetrafluoroethylliner liner, add 2mmol methyl ethyl diketone vanadyl title complex, and adding 45ml water, the hydrochloric acid that the back adds 0.5ml 1mol/L is dissolved in the acidic aqueous solution methyl ethyl diketone vanadyl fully, stirs 30min then in air.Be placed on 200 ℃ the interior insulation of baking oven 30h behind the sealing hydro-thermal autoclave.Behind the naturally cooling, use the product of deionized water, absolute ethanol washing gained respectively, remove possible impurity.Fig. 4 is according to the FE-SEM photo that is implemented the resulting smooth nano belt of example.This programme is applicable to following combination simultaneously: 2mmol methyl ethyl diketone vanadium complex+45ml water+0.5ml 1mol/L sulfuric acid; The adjacent vanillic acid vanadyl of 2mmol title complex+45ml water+0.5ml 1mol/L hydrochloric acid or sulfuric acid; 2mmol VCl4+45ml water+0.5ml 1mol/L hydrochloric acid; 2mmol VOSO4+45ml water+0.5ml 1mol/L sulfuric acid; 2mmol VS2+1ml 1mol/L ammoniacal liquor or sodium hydroxide.This figure illustrates that different precursors obtains the different-shape of material of the same race under different reaction conditionss, illustrate that its pattern is adjustable, controlled.In addition from shape appearance figure except its size range, degree of uniformity as can be seen, can also be by crystalline structure its growth orientation of explanation of setting out.
Embodiment 3
Nanometer monocline phase VO
2(VO
2(M)) realization of powder body material nanometer hexagonal flower: in the 50ml polytetrafluoroethylliner liner, add 2mmol VOOH, and adding 45ml water, the hydrochloric acid that the back adds 1ml 1mol/L is dissolved in the aqueous solution VOOH fully, adds the nitric acid of 3ml 0.1mol/L then, and stir 10min in air.Be placed on 200 ℃ the interior insulation of baking oven 30h behind the sealing hydro-thermal autoclave.Behind the naturally cooling, use the product of deionized water, absolute ethanol washing gained respectively, remove possible impurity.Fig. 5 is according to the flower-shaped FE-SEM photo of the hexagonal of present embodiment products therefrom.This experimental program is applicable to following combination simultaneously: 2mmol V (OH) 2NH2+45ml water+2ml 0.1mol/L nitric acid or hydrogen peroxide; 2mmol V2O3+1ml nitric acid+45ml water+2ml 0.1mol/L hydrogen peroxide; 2mmol methyl ethyl diketone vanadium complex+45ml water+2ml0.1mol/L nitric acid.This figure illustrates that different precursors obtains the different-shape of material of the same race under different reaction conditionss, illustrate that its pattern is adjustable, controlled.In addition from shape appearance figure except its size range, degree of uniformity as can be seen, can also be by crystalline structure its growth orientation of explanation of setting out.
From the photo of embodiment 1,2 and 3 gained nanometer products, the products therefrom particle form is rule, and size range is less, can have better industrial use.
Embodiment 4
Monocline phase VO
2(VO
2(M)) realization of powder dopant material:
In the 50ml polytetrafluoroethylliner liner, add 2mmol metavanadic acid ammonia (NH
4VO
3) and 0.2mmol ortho-tungstic acid and add 45ml water, the ammoniacal liquor that the back adds 1ml 1mol/L makes the two disperse and be dissolved in fully in the alkaline aqueous solution, adds the 1ml hydrazine hydrate then, stirs 10min.Be placed on 200 ℃ the interior insulation of baking oven 30h behind the sealing hydro-thermal autoclave.Behind the naturally cooling, use the product of deionized water, absolute ethanol washing gained respectively, remove possible impurity.Obtain adulterated VO so easily
2(M) powder body material.The transformation temperature of adulterated powder can be reduced to 20 degree from simple 68 degree, can satisfy the different intelligent temperature requirements like this.This experimental program is applicable to simultaneously at embodiment 1,2, adds the compound or the ion of tungstenic between 0.1%～10% (and the mol ratio in vanadium source) in 3, the compound or the ion that contain molybdenum, manganiferous compound or ion, manganiferous compound or ion, titaniferous compound or ion or their combination.
The result of above analysis and characterization proves that the present embodiment products therefrom is vanadium dioxide and the adulterated powder thereof with intelligent power saving performance, is the very important thermochromic material that has application prospect of a class.
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 (9)
1. Hydrothermal Preparation has the method for the vanadium dioxide of intelligent power saving performance, it is characterized in that: in the water heating kettle that the vanadium source aqueous solution is housed, add oxidation, reduction or acid-base modifier, the concentration of described vanadium source in the aqueous solution is more than the 0.001mol/L, and described vanadium source comprises metavanadic acid ammonia, sodium orthovanadate, Vanadium Pentoxide in FLAKES, potassium metavanadate, vanadium oxytrichloride, vanadium tetrachloride, vanadylic sulfate, methyl ethyl diketone vanadyl title complex, o-vanillin vanadyl title complex, vanadium trichloride, V
2S
5, VS
2, VOOH, V (OH)
2NH
2, V
2O
3, methyl ethyl diketone vanadium complex and their combination, described oxidation, reduction or acid-base modifier comprise oxidisability soda acid, reductibility soda acid, non-oxide, reductibility soda acid or have other materials of oxidation, reductibility and their combination; Then with described water heating kettle as in 40 ℃-300 ℃ the baking oven insulation 30 minutes-5 days, after reacting completely, centrifugal collection obtains vanadium dioxide.
2. Hydrothermal Preparation according to claim 1 has the method for the vanadium dioxide of intelligent power saving performance, it is characterized in that: when described vanadium source is selected from metavanadic acid ammonia, sodium orthovanadate, Vanadium Pentoxide in FLAKES, potassium metavanadate, vanadium oxytrichloride, V
2S
5The time, described oxidation, reduction or acid-base modifier are selected from the reductibility soda acid or have other materials of reductibility and their combination, and collecting the vanadium dioxide that obtains is even overlong nanowire.
3. Hydrothermal Preparation according to claim 1 has the method for the vanadium dioxide of intelligent power saving performance, it is characterized in that: when described vanadium source is selected from vanadium tetrachloride, vanadylic sulfate, methyl ethyl diketone vanadyl title complex, VS
2, during o-vanillin vanadyl title complex, described oxidation, reduction or acid-base modifier are selected from non-oxide reductibility soda acid, collecting the vanadium dioxide that obtains is ganoid nano belt.
4. Hydrothermal Preparation according to claim 1 has the method for the vanadium dioxide of intelligent power saving performance, it is characterized in that: when described vanadium source is selected from VOOH, V (OH)
2NH
2, V
2O
3, when vanadium trichloride, methyl ethyl diketone vanadium complex, described oxidation, reduction or acid-base modifier are selected from the oxidisability soda acid or have other materials of oxidisability and their combination, collecting the vanadium dioxide that obtains is that hexagonal is flower-shaped.
5. Hydrothermal Preparation according to claim 1 has the method for the vanadium dioxide of intelligent power saving performance, it is characterized in that: when described oxidation, reduction or acid-base modifier are selected from the reductibility soda acid or have other materials of reductibility, be hydrazine hydrate, formic acid, lactic acid, sodium borohydride and their combination.
6. Hydrothermal Preparation according to claim 1 has the method for the vanadium dioxide of intelligent power saving performance, it is characterized in that: when described oxidation, reduction or acid-base modifier are selected from non-oxide reductibility soda acid, be dilute hydrochloric acid, dilute sulphuric acid, ammoniacal liquor, sodium hydroxide solution and their combination.
7. Hydrothermal Preparation according to claim 1 has the method for the vanadium dioxide of intelligent power saving performance, it is characterized in that: when described oxidation, reduction or acid-base modifier are selected from the oxidisability soda acid or have other materials of oxidisability, be rare nitric acid, hydrogen peroxide and their combination.
8. Hydrothermal Preparation according to claim 1 has the method for the vanadium dioxide of intelligent power saving performance, it is characterized in that: be mixed with in the compound or the ion of tungstenic, the compound that contains molybdenum or ion, manganiferous compound or ion, the compound that contains chromium or ion, titaniferous compound or the ion one or more in the aqueous solution of described vanadium source, and doping is adjustable between 0.1%～10% mol ratio.
9. have the method for the vanadium dioxide of intelligent power saving performance according to one of any described Hydrothermal Preparation of claim 1-4, it is characterized in that: the metal-insulator phase transition temperature of described vanadium dioxide is
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| CN101391814B (en) * | 2008-10-31 | 2012-01-25 | 中国科学院上海硅酸盐研究所 | Method for preparing rutile phase hypovanadic oxide powder |
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