CN101880060B - Method for quickly preparing monoclinic phase VO2 - Google Patents
Method for quickly preparing monoclinic phase VO2 Download PDFInfo
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- CN101880060B CN101880060B CN 201010231179 CN201010231179A CN101880060B CN 101880060 B CN101880060 B CN 101880060B CN 201010231179 CN201010231179 CN 201010231179 CN 201010231179 A CN201010231179 A CN 201010231179A CN 101880060 B CN101880060 B CN 101880060B
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Abstract
The invention discloses a method for quickly preparing monoclinic phase VO2. In the method, metastable phase reactant containing vanadium or VOOH reactant reacts for 1 minute to 12 hours at the temperature of 200-500 DEG C in the atmosphere of inert gases or inert gases doped with oxygen, and the monoclinic phase VO2 is obtained after cooling. The method can quickly convert the metastable phase reactant containing vanadium or VOOH into the monoclinic phase VO2 under the protection of normal-pressure inert atmosphere. The method has simple technology, low cost, high yield and favorable purity and can quickly prepare the intelligent energy-saving monoclinic phase VO2 powder on a large scale.
Description
Technical field
The present invention relates to the preparation of monoclinic phase and cubic rutile phase hypovanadic oxide powder, especially relate to a kind of monoclinic phase VO for preparing fast
2method.
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 larger variation on optical characteristics.Especially vanadium dioxide (VO
2) be subject to especially people and pay close attention to especially.
Monoclinic phase VO
2(referred to as VO
2) and cubic Rutile Type VO (M)
2(referred to as VO
2(R)) powder, can cause it to external world by phase transformation, as sunlight infrared rays part, carries out intelligent control and realize intelligent power saving.Monocrystalline VO
2the metal-insulator phase transition temperature be 68 ℃.At this temperature, VO
2crystalline structure can be from high temperature Tetragonal rutile structure (metalline) to monoclinic phase (isolator character) under low temperature, change, the transformation of crystalline structure is accompanied by the sudden change of light, electrical property.Tetragonal from high temperature is to the monoclinic phase under low temperature, VO
2infrared transmittivity sharply raise, and the above sudden change of 5 magnitudes occurs in the direct current resistance coefficient.
VO
2the special property of this metal-insulator phase transition make it at aspects such as photoelectric conversion material, optical storage, laser radiation and form solar controls, potential application be arranged.VO
2be a kind of typical material that infrared rays carries out perception and regulation and control to external world, monoclinic phase (low-temperature phase) has the infrared function seen through, and Tetragonal (high-temperature-phase) has the ultrared characteristic of obstruct, can be 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, have extremely wide intelligent power saving application prospect.Along with the further understanding of people to its rule of color change, particularly by variable color stability and temperature susceplibility are further improved, will greatly widen its Application Areas and application mode, produce significant Social benefit and economic benefit.
Up to the present, the hypovanadic oxide powder (VO that there is the intelligent power saving performance
2and VO (M)
2(R) phase) prepare more common method and realize (>12 hours) for long term annealing under the vapor deposition apparatus at logical hydrogen or inert atmosphere.This method needs expensive cost to be difficult to control the valence state of vanadium wherein simultaneously, is difficult to obtain VO
2pure phase.This makes monoclinic phase and cubic rutile phase hypovanadic oxide (VO
2and VO (M)
2(R)) preparation cost of powder improves greatly, is difficult to accomplish scale production.
Summary of the invention
The purpose of this invention is to provide a kind of monoclinic phase VO for preparing
2method.
A kind of monoclinic phase VO for preparing provided by the invention
2method, comprise the steps: metastable phase is reacted containing the vanadium reactant in inert atmosphere, obtain described monoclinic phase VO after cooling
2;
In described reactions steps, temperature is 200-500 ℃, and the time is 1 minute-12 hours.
In the reactions steps of aforesaid method, temperature is preferably 400-450 ℃, and more preferably 450 ℃, the time is preferably 1 minute-4 hours, and more preferably 1 minute-30 minutes, especially preferably 1 minute; Described inert atmosphere is nitrogen and/or argon gas atmosphere; Described metastable phase is selected from the metastable phase vanadium dioxide containing the vanadium reactant and (is abbreviated as VO
2(B)), A phase VO
2(be abbreviated as VO
2(A)), paramontroseite (is abbreviated as VO
2or VO (P)
2) and VO (paramontroseite)
2.H
2at least one in O.This reaction is annealing reaction, and annealing device used can be sectional type tube furnace or common gaseous phase deposition stove commonly used in this area.
Preparation provided by the invention is doped with the monoclinic phase VO of metallic element
2method, comprise the steps: the metastable phase doped with metallic element is reacted containing the vanadium reactant in inert atmosphere, obtain the monoclinic phase VO of described doped metallic elements after cooling
2;
Described metallic element is selected from least one in Mn, Ti, Cr, Mo and W;
In described reactions steps, temperature is 200-500 ℃, and the time is 1 minute-12 hours.
In the reactions steps of aforesaid method, temperature is preferably 400-450 ℃, and more preferably 450 ℃, the time is preferably 1 minute-4 hours, more preferably 1 minute; Reaction pressure is normal pressure; Described inert atmosphere is nitrogen and/or argon gas atmosphere; Described metastable phase is selected from metastable phase vanadium dioxide, A phase VO containing the vanadium reactant
2, paramontroseite and VO
2.H
2at least one in O; This reaction is annealing reaction, and annealing device used can be sectional type tube furnace or common gaseous phase deposition stove commonly used in this area.
Another kind provided by the invention prepares monoclinic phase VO
2method, comprise the steps: the VOOH reactant is reacted in containing the inert atmosphere of oxygen, obtain described monoclinic phase VO after cooling
2;
In described reactions steps, temperature is 200-500 ℃, and the time is 1 minute-12 hours.
In the reactions steps of the method, temperature is 200-500 ℃, preferred 400-450 ℃, and more preferably 400 ℃, the time is preferably 1 minute-4 hours, and more preferably 0.5 hour-6 hours, especially preferably 0.5 hour; Reaction pressure is normal pressure; Described inert atmosphere is nitrogen and/or argon gas atmosphere, and the volume percent of described oxygen in the described inert atmosphere that contains oxygen is 5-10%; Described VOOH reactant be selected from lepidocrocite (be abbreviated as VOOH (L) or LepidoricoteVOOH), at least one in hollandite (being abbreviated as VOOH (H) or Hollandite VOOH) and montroseite (being abbreviated as VOOH (M) or Montroseite VOOH); This reaction is annealing reaction, and annealing device used can be sectional type tube furnace or common gaseous phase deposition stove commonly used in this area.
Preparation provided by the invention is doped with the monoclinic phase VO of metallic element
2method, comprise the steps: the VOOH reactant doped with metallic element is reacted in containing the inert atmosphere of oxygen, obtain the monoclinic phase VO of described doped metallic elements after cooling
2;
Described metallic element is selected from least one in Mn, Ti, Cr, Mo and W;
In described reactions steps, temperature is 200-500 ℃, and the time is 1 minute-12 hours.
In the described reactions steps of the method, temperature is preferably 400-450 ℃, and more preferably 400 ℃, the time is preferably 1 minute-4 hours, more preferably 30 minutes; Reaction pressure is normal pressure; Described inert atmosphere is nitrogen and/or argon gas atmosphere, and the volume percent of described oxygen in the described inert atmosphere that contains oxygen is 5-10%, preferably 5%; Described VOOH reactant is selected from least one in lepidocrocite, hollandite and montroseite.This reaction is annealing reaction, and annealing device used can be sectional type tube furnace or common gaseous phase deposition stove commonly used in this area.
In four kinds of preparation methods that the invention described above provides, described metastable phase vanadium-containing compound can obtain according to various ordinary method preparations, as be prepared as follows: the aqueous solution of vanadium-containing compound is reacted with reaction reagent, react the complete described metastable phase vanadium dioxide that obtains; Described reaction reagent is selected from least one in rare nitric acid, hydrogen peroxide, hydrazine hydrate aqueous solution, aqueous formic acid, lactic acid aqueous solution, sodium borohydride aqueous solution, dilute hydrochloric acid, dilute sulphuric acid, thioacetyl amine aqueous solution, ammoniacal liquor and aqueous sodium hydroxide solution, and the mass percentage concentration of above-mentioned each reaction reagent aqueous solution preferably is 10%; Described vanadium-containing compound is selected from 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, V (OH)
2nH
2, V
2o
3with at least one in the methyl ethyl diketone vanadium complex; In described reactions steps, temperature is 40 ℃-220 ℃, preferred 150-200 ℃, and the time is 30 minutes-48 hours, the time is preferably 6 hours-12 hours; The concentration of the aqueous solution of described vanadium-containing compound is 0.001-0.8mol/L, preferred 0.05-0.8mol/L, and in described vanadium-containing compound and described reaction reagent, the amount ratio of acid or alkali is 0.5-10mmol: 0.1-2.5mmol, preferably 1.5-3mmol: 0.5-1mmol.This reaction is hydro-thermal reaction, and hydro-thermal reaction device used can be various industrial stainless steel still reaction unit commonly used in this area, as hydro-thermal autoclave or glass reflux.
The described vanadium-containing compound of the metastable phase doped with metallic element can obtain according to various ordinary method preparations, as be prepared as follows: vanadium-containing compound and metal-salt are reacted with reaction solvent in water, react the complete described vanadium dioxide of the metastable phase doped with metallic element that obtains; Wherein, described reaction reagent is selected from least one in rare nitric acid, hydrogen peroxide, hydrazine hydrate aqueous solution, aqueous formic acid, lactic acid aqueous solution, sodium borohydride aqueous solution, dilute hydrochloric acid, dilute sulphuric acid, thioacetyl amine aqueous solution, ammoniacal liquor and aqueous sodium hydroxide solution, and the mass percentage concentration of above-mentioned each reaction reagent aqueous solution preferably is 10%; Described vanadium-containing compound is selected from 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, V (OH)
2nH
2, V
2o
3with at least one in the methyl ethyl diketone vanadium complex; Described metal-salt is selected from the salt of following at least one metallic element: Mn, Ti, Cr, Mo and W; In described reactions steps, temperature is 40 ℃-200 ℃, preferred 150-200 ℃, and the time is 30 minutes-48 hours, the time is preferably 6 hours-12 hours; The concentration 0.001-0.2mol/L of the aqueous solution of described vanadium-containing compound, preferred 0.01mol/L, in described vanadium-containing compound, described metal-salt and described reaction reagent, the amount ratio of acid or alkali is 0.5-10mmol: 0.001-0.5mmol: 0.1-2mmol, preferably 1.5-3mmol: 0.015-0.15mmol: 0.5-1mmol.This reaction is hydro-thermal reaction, and hydro-thermal reaction device used can be various industrial stainless steel still reaction unit commonly used in this area, as hydro-thermal autoclave or glass reflux.
Described VOOH reactant can obtain according to various ordinary method preparations, as be prepared as follows: the aqueous solution of vanadium-containing compound is reacted with reaction reagent, react the complete described VOOH reactant that obtains; Described reaction reagent is selected from least one in rare nitric acid, hydrogen peroxide, hydrazine hydrate aqueous solution, aqueous formic acid, lactic acid aqueous solution, sodium borohydride aqueous solution, dilute hydrochloric acid, dilute sulphuric acid, thioacetyl amine aqueous solution, ammoniacal liquor and aqueous sodium hydroxide solution, and the mass percentage concentration of above-mentioned each reaction reagent aqueous solution preferably is 10%; Described vanadium-containing compound is selected from 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, V
2s
5, VS
2, V (OH)
2nH
2with at least one in the methyl ethyl diketone vanadium complex; In described reactions steps, temperature is 40 ℃-200 ℃, preferred 40-200 ℃, and the time is 30 minutes-48 hours, the time is preferably 6 hours-12 hours; The concentration of the aqueous solution of described vanadium-containing compound is 0.001-0.2mol/L, preferred 0.01mol/L, and in described vanadium-containing compound and described reaction reagent, the amount ratio of acid or alkali is 0.5-10mmol: 0.1-2mmol, preferably 1.5-3mmol: 0.5-1mmol.This reaction is hydro-thermal reaction, and hydro-thermal reaction device used can be various industrial stainless steel still reaction unit commonly used in this area, as hydro-thermal autoclave or glass reflux.
The described reactant of the VOOH doped with metallic element can obtain according to various ordinary method preparations, as be prepared as follows: vanadium-containing compound and metal-salt are reacted with reaction solvent in water, react the complete described reactant of the VOOH doped with metallic element that obtains; Wherein, described reaction reagent is selected from least one in rare nitric acid, hydrogen peroxide, hydrazine hydrate aqueous solution, aqueous formic acid, lactic acid aqueous solution, sodium borohydride aqueous solution, dilute hydrochloric acid, dilute sulphuric acid, thioacetyl amine aqueous solution, ammoniacal liquor and aqueous sodium hydroxide solution, and the mass percentage concentration of above-mentioned each reaction reagent aqueous solution preferably is 10%; Described vanadium-containing compound is selected from 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, V (OH)
2nH
2, V
2o
3with at least one in the methyl ethyl diketone vanadium complex; Described metal-salt is selected from the salt of following at least one metallic element: Mn, Ti, Cr, Mo and W;
In described reactions steps, temperature is 40 ℃-200 ℃, preferred 40-200 ℃, and the time is 30 minutes-48 hours, the time is preferably 6 hours-12 hours; The concentration of the aqueous solution of described vanadium-containing compound is 0.001-0.2mol/L, preferred 0.01mol/L, and in described vanadium-containing compound and described reaction reagent, the amount ratio of acid or alkali is 0.5-10mmol: 0.1-2mmol, preferably 1.5-3mmol: 0.5-1mmol.This reaction is hydro-thermal reaction, and hydro-thermal reaction device used can be various industrial stainless steel still reaction unit commonly used in this area, as hydro-thermal autoclave or glass reflux.
In above-mentioned four kinds of preparation methods, described A phase VO
2(A) can prepare by the following method and obtain: adding 2mmol VO (acac) in the tetrafluoroethylene reactor that is 50ml at volume
2with 40mL distilled water, and the HCOOH aqueous solution 1mmol that is 10% by mass percentage concentration to regulate pH value be 3～4, after stirring 30min, in the still shell of packing into, seal, after keep 12h under 220 ℃, centrifugal collection product after naturally cooling, obtain A phase VO
2(A).
Described metastable phase VO
2(B) can prepare by the following method and obtain: in the tetrafluoroethylene reactor that is 50mL at volume, adding 2mmol V
2o
5with 40mL distilled water, and the HCOOH aqueous solution 1mmol that is 10% by mass percentage concentration to regulate pH value be 3～4, after stirring 30min, in the still shell of packing into, seal, then maintenance 12 hours under 200 ℃, after naturally cooling, centrifugal collection product obtains metastable phase VO
2(B).
Described VO
2(P) (paramontroseite) can prepare by the following method and obtain: in the tetrafluoroethylene reactor that is 50ml at volume, adding 4mmol Na
3vO
412H
2o, 20mmol TAA (thioacetamide) and 50ml distilled water after stirring 30min, in the still shell of packing into, then keep 12h under 200 ℃, and after naturally cooling, centrifugal collection product, obtain above-mentioned VO
2(P) (paramontroseite).
Described VOOH (L) can prepare by the following method and obtain: add 2mmol metavanadic acid ammonia and 35ml distilled water in the tetrafluoroethylene reactor that is 50ml at volume, after add the ammoniacal liquor that the 8ml mass percentage concentration is 10%, after stirring 30min, pack in still shell and seal, after keep 12h under 200 ℃, after naturally cooling, centrifugal collection product, obtain described VOOH (L).
Described VOOH (H) can prepare by the following method and obtain: add 2mmol metavanadic acid ammonia and 35ml distilled water in the tetrafluoroethylene reactor that is 50ml at volume, after add 1ml 1M HCl that it is dissolved fully, after add the hydrazine hydrate aqueous solution that the 3ml mass percentage concentration is 10%, stir 30min after centrifugal collection obtain V (OH)
2nH
2.Rear itself and 1mmol NH
4f mixes and to be placed in the polytetrafluoroethylliner liner that 35ml distilled water is housed, after pack in still shell and seal, keep 12h under 200 ℃, after naturally cooling, centrifugal collection product, obtain described VOOH (H).
Described VOOH (M) can prepare by the following method and obtain: add 2mmol sodium orthovanadate, 2mmol thioacetamide, 0.5mmol NH in the tetrafluoroethylene reactor that is 50ml at volume
4f and 35ml distilled water, seal in the still shell of packing into after stirring 30min, under 200 ℃, keeps 12h, and after naturally cooling, centrifugal collection product, obtain described VOOH (M).
The invention described above provides prepares monoclinic phase VO
2the reaction mechanism of method is: the metastable phase vanadium-containing compound can be to stable VO under inert atmosphere and hot conditions
2(R) change mutually, finally change after cooling monoclinic phase VO into
2(VO
2(M)), and the VOOH reactant is mixing under the inert atmosphere that appropriate oxygen is arranged, and oxidation and inversion of phases occur simultaneously, and is attended by deviating from of water, the cooling rear VO that finally changes into
2(M).
The monoclinic phase VO for preparing provided by the invention
2with the monoclinic phase VO doped with metallic element
2method, can be under the normal pressure inert atmosphere protection, by metastable phase vanadium dioxide or new phase VOOH rapid conversion, be monoclinic phase VO
2.The method technique is simple, cost is low, productive rate is high, purity is good, and can prepare fast in enormous quantities hypovanadic oxide powder (the VO of intelligent power saving performance
2(M) phase), the atom transformation efficiency is 100% (be vanadium atom can be converted into the vanadium atom in product fully) in each precursor.This monoclinic phase VO
2the metal-insulator phase transition temperature be 20 ℃～68 ℃.The various VO of the monoclinic phase doped with metallic element
2in, the purpose of Doped Tungsten, molybdenum, chromium and manganese is to change transformation temperature; The purpose of Doped with Titanium is to strengthen visible light transmissivity.Specifically, the method has the following advantages:
1, applicable vanadium of the present invention source is wider, through hydro-thermal reaction, can prepare metastable phase vanadium dioxide precursor and the VOOH precursor that purity is very high, the precursor VO that the gained high purity has intelligent power saving character after annealing
2(M).
2, due to the suitable selection to precursor, in the present invention, annealing time shortens greatly than traditional annealing time, the shortlyest can realize that at one minute metastable phase vanadium dioxide precursor is to having intelligent power saving character VO
2(M) rapid conversion, shortened the reaction times greatly, reduced the consumption of the energy, and lay a good foundation for a large amount of suitability for industrialized production, has wide industrial prospect.
3, the monoclinic phase VO that utilizes present method to be synthesized
2powder has very superior intelligent power saving cycle performance; intelligence transformation temperature zone has been contained from 20 ℃～68 ℃; can extensively meet the requirement of the aspects such as photoelectric conversion material, optical storage, laser radiation and form solar control, be suitable for further application in daily life from now on and industrial production.
The accompanying drawing explanation
Fig. 1 is gained paramontroseite VO in embodiment 3
2(P) XRD figure spectrum.
Fig. 2 is the XRD figure spectrum that embodiment 11 prepares gained montroseite (Montroseite VOOH).
The XRD figure spectrum of the hollandite that Fig. 3 is gained in embodiment 9 (Hollandite VOOH).
Fig. 4 is that embodiment 3 prepares gained monoclinic phase VO
2(M) XRD figure spectrum.
Fig. 5 is that embodiment 3 prepares gained monoclinic phase VO
2(M) DSC circulation collection of illustrative plates.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but the present invention is not limited to following examples.Described in following embodiment, method if no special instructions, is ordinary method.Described conversion unit if no special instructions, is conventional equipment.
Embodiment 1: use VO
2(B) prepare VO
2(M)
1) in the tetrafluoroethylene reactor that is 50mL at volume, add 2mmol V
2o
5with 40mL distilled water, and the HCOOH aqueous solution that is 10% by mass percentage concentration adjusting pH value is 3～4.After stirring 30min, in the still shell of packing into, seal, then keep 12 hours under 200 ℃, after naturally cooling, centrifugal collection product obtains VO
2(B).
2) will fill 0.5g VO
2(B) porcelain boat is placed in and is connected with N
2tube furnace in, and the 12h that anneals under 450 ℃, obtain the VO that purity is 100% after cooling
2(M).Shown in the XRD spectra of this compound and DSC circulation collection of illustrative plates and Fig. 4 and Fig. 5 without substantive difference.As seen from the figure, this compound structure is correct.
Embodiment 2: with A phase VO
2(A) prepare VO
2(M)
1) add 2mmol VO (acac) in the tetrafluoroethylene reactor that is 50ml at volume
2(methyl ethyl diketone vanadyl title complex) and 40mL distilled water, and the HCOOH aqueous solution that is 10% by mass percentage concentration to regulate pH value be 3～4, after stirring 30min, pack in still shell and seal, after keep 12h under 220 ℃, centrifugal collection product after naturally cooling, obtain A phase VO
2(A).
2) will fill 0.5g VO
2(A) porcelain boat is placed in and is connected with N
2tube furnace in, and the 12h that anneals under 450 ℃, obtain the VO that purity is 100% after cooling
2(M).Shown in the XRD spectra of this compound and DSC circulation collection of illustrative plates and Fig. 4 and Fig. 5 without substantive difference.As seen from the figure, this compound structure is correct.
Embodiment 3: use VO
2(P) prepare VO
2(M)
1) in the tetrafluoroethylene reactor that is 50ml at volume, add 4mmol Na
3vO
412H
2o (sodium orthovanadate), 20mmol TAA (thioacetamide) and 50ml distilled water after stirring 30min, in the still shell of packing into, then keep 12h under 200 ℃, and after naturally cooling, centrifugal collection product, obtain VO
2(P), the XRD spectra of this compound as shown in Figure 1.As seen from the figure, this compound structure is correct.
2) will fill 0.5g VO
2(P) porcelain boat is placed in and is connected with N
2tube furnace in, and annealing 1 minute under 400 ℃, obtain the VO that purity is 100% after cooling
2(M).This compound VO
2(M) XRD spectra and DSC circulation collection of illustrative plates are respectively shown in Fig. 4 and Fig. 5.As seen from the figure, this compound structure is correct.
Embodiment 4: with the VO that mixes Mo
2(B) prepare VO
2(M)
1) in the tetrafluoroethylene reactor that is 50ml at volume, add 2mmol V
2o
5, 0.25mmol Na
2moO
4with 4mmol H
2c
2o
42H
2o, after add 40ml distilled water, after stirring 30min, in the still shell of packing into, seal, after keep 24h under 200 ℃, after naturally cooling, centrifugal collection product, obtain mixing the VO of Mo
2(B).
2) will fill the VO that 0.5g mixes Mo
2(B) porcelain boat is placed in and is connected with N
2tube furnace in and under 450 ℃, annealing 12h, obtain the VO that mixes Mo that purity is 100% after cooling
2(M).Shown in the XRD spectra of this compound and DSC circulation collection of illustrative plates and Fig. 4 and Fig. 5 without substantive difference.As seen from the figure, this compound structure is correct.
Embodiment 5: with the VO that mixes W
2(B) prepare VO
2(M)
1) in the tetrafluoroethylene reactor that is 50ml at volume, add 2mmol V
2o
5, 0.25mmol Na
2wO
4with 4mmol H
2c
2o
42H
2o, after add 40ml distilled water, after stirring 30min, in the still shell of packing into, seal, after keep 24h under 200 ℃, after naturally cooling, centrifugal collection product, obtain mixing the VO of W
2(B).
2) will fill the VO that 0.5g mixes W
2(B) porcelain boat is placed in and is connected with N
2tube furnace in, and the 12h that anneals under 450 ℃, obtain the VO that mixes W that purity is 100% after cooling
2(M).Shown in the XRD spectra of this compound and DSC circulation collection of illustrative plates and Fig. 4 and Fig. 5 without substantive difference.As seen from the figure, this compound structure is correct.
Embodiment 6: with the VO that mixes Ti
2(B) prepare VO
2(M)
1) in the tetrafluoroethylene reactor that is 50ml at volume, add 2mmol V
2o
5, 0.25mmolK
2tiO (C
2o
4)
2with 4mmol H
2c
2o
42H
2o, after add 40ml distilled water, after stirring 30min, in the still shell of packing into, seal, after keep 24h under 200 ℃, after naturally cooling, centrifugal collection product, obtain mixing the VO of Ti
2(B).
2) will fill the VO that 0.5g mixes Ti
2(B) porcelain boat is placed in and is connected with N
2tube furnace in, and the 12h that anneals under 450 ℃, obtain the VO that mixes Ti that purity is 100% after cooling
2(M).Shown in the XRD spectra of this compound and DSC circulation collection of illustrative plates and Fig. 4 and Fig. 5 without substantive difference.As seen from the figure, this compound structure is correct.
Embodiment 7: with the VO that mixes Mn
2(B) prepare VO
2(M)
1) in the tetrafluoroethylene reactor that is 50ml at volume, add 2mmol V
2o
5, 0.25mmol MnCO
3with 4mmol H
2c
2o
42H
2o, after add 40ml distilled water, after stirring 30min, in the still shell of packing into, seal, after keep 24h under 200 ℃, after naturally cooling, centrifugal collection product, obtain mixing the VO of Mn
2(B).
2) will fill the VO that 0.5g mixes Mn
2(B) porcelain boat is placed in and is connected with N
2tube furnace in, and the 12h that anneals under 450 ℃, obtain the VO that mixes Mn that purity is 100% after cooling
2(M).Shown in the XRD spectra of this compound and DSC circulation collection of illustrative plates and Fig. 4 and Fig. 5 without substantive difference.As seen from the figure, this compound structure is correct.
Embodiment 8: with VOOH (L), prepare VO
2(M)
1) add 2mmol metavanadic acid ammonia and 35ml distilled water in the tetrafluoroethylene reactor that is 50ml at volume, after add the ammoniacal liquor that the 8ml mass percentage concentration is 10%, after stirring 30min, pack in still shell and seal, after keep 12h under 200 ℃, after naturally cooling, centrifugal collection product, obtain VOOH (L).
The porcelain boat that 2) will fill 0.5g VOOH (L) is placed in the tube furnace that is connected with oxygen and nitrogen mixture (wherein the volume percent of oxygen is 5%), and the 6h that anneals under 400 ℃, obtains the VO that purity is 100% after cooling
2(M).Shown in the XRD spectra of this compound and DSC circulation collection of illustrative plates and Fig. 4 and Fig. 5 without substantive difference.As seen from the figure, this compound structure is correct.
Embodiment 9: with Hollandite VOOH, prepare VO
2(M)
1) add 2mmol metavanadic acid ammonia and 35ml distilled water in the tetrafluoroethylene reactor that is 50ml at volume, after add 1ml 1M HCl that it is dissolved fully, after add the hydrazine hydrate aqueous solution that the 3ml mass percentage concentration is 10%, stir 30min after centrifugal collection obtain V (OH)
2nH
2.Then by gained V (OH)
2nH
2with 1mmol NH
4the F mixing is placed in the polytetrafluoroethylliner liner that 35ml distilled water is housed, and in the still shell of packing into, seals, and under 200 ℃, keeps 12h, and after naturally cooling, centrifugal collection product, obtain Hollandite VOOH.The XRD figure spectrum of this compound as shown in Figure 3.As seen from the figure, this compound structure is correct.
The porcelain boat that 2) will fill 0.5g Hollandite VOOH is placed in the tube furnace that is connected with oxygen and nitrogen mixture (wherein the volume percent of oxygen is 5%), and the 30min that anneals under 400 ℃, obtains the VO that purity is 100% after cooling
2(M).The XRD figure spectrum of this compound and Fig. 2 are without substantive difference.As seen from the figure, this compound structure is correct.
Embodiment 10: with the Hollandite VOOH that mixes tungsten, prepare VO
2(M)
1) add 2mmol metavanadic acid ammonia and 35ml distilled water in the tetrafluoroethylene reactor that is 50ml at volume, after add 1ml 1M HCl that it is dissolved fully, add the hydrazine hydrate aqueous solution that the 3ml mass percentage concentration is 10%, after stirring 30min, centrifugal collection obtains V (OH) again
2nH
2after, by V (OH)
2nH
2with 1mmol NH
4f and the mixing of 0.1mmol sodium wolframate are placed in the polytetrafluoroethylliner liner that 35ml distilled water is housed, and in the still shell of packing into, seal, and under 200 ℃, keep 12h, and after naturally cooling, centrifugal collection product, obtain the Hollandite VOOH doped with tungsten.This compound XRD figure spectrum with Fig. 3 without substantive difference.As seen from the figure, this compound structure is correct.
2) will fill 0.5g and be placed in doped with the porcelain boat of the Hollandite VOOH of tungsten the tube furnace that is connected with oxygen and nitrogen mixture (wherein the volume percent of oxygen is 5%), and the 30min that anneals under 400 ℃, obtain the VO doped with tungsten that purity is 100% after cooling
2(M).The XRD figure spectrum of this compound and Fig. 2 are without substantive difference.As seen from the figure, this compound structure is correct.
Embodiment 11: with Montroseite VOOH, prepare VO
2(M)
1) add 2mmol sodium orthovanadate, 2mmol thioacetamide, 0.5mmol NH in the tetrafluoroethylene reactor that is 50ml at volume
4f and 35ml distilled water, seal in the still shell of packing into after stirring 30min, under 200 ℃, keeps 12h, and after naturally cooling, centrifugal collection product, obtain Montroseite VOOH.
The porcelain boat that 2) will fill 0.5g Montroseite VOOH is placed in the tube furnace that is connected with oxygen and nitrogen mixture (wherein the volume percent of oxygen is 5%), and the 30min that anneals under 400 ℃, obtains the VO that purity is 100% after cooling
2(M).This compound XRD figure spectrum as shown in Figure 2.As seen from the figure, this compound structure is correct.
The result of above analysis and characterization proves, the present embodiment has universality within the specific limits, and 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 by claims and be equal to and limit.
Claims (8)
1. one kind prepares monoclinic phase VO
2method, comprise the steps: the VOOH reactant is reacted in containing the inert atmosphere of oxygen, obtain described monoclinic phase VO after cooling
2; The volume percent of described oxygen in the described inert atmosphere that contains oxygen is 5-10%; In described reactions steps, temperature is 200-500 ℃, and the time is 1 minute-12 hours.
2. method according to claim 1, it is characterized in that: in described reactions steps, temperature is 400-450 ℃, the time is 1 minute-4 hours; Described inert atmosphere is nitrogen and/or argon gas atmosphere.
3. method according to claim 1 and 2, it is characterized in that: described VOOH reactant is selected from least one in lepidocrocite, hollandite and montroseite;
Described VOOH reactant is to obtain according to comprising the steps the method preparation: the aqueous solution of vanadium-containing compound is reacted with reaction reagent, react the complete described VOOH reactant that obtains; Described reaction reagent is hydrazine hydrate aqueous solution, thioacetyl amine aqueous solution or ammoniacal liquor; Described vanadium-containing compound is ammonium meta-vanadate or sodium orthovanadate; In the preparation feedback step of described VOOH reactant, temperature is that 40 ℃-200 ℃ times are 30 minutes-48 hours; The concentration of the aqueous solution of described vanadium-containing compound is 0.001-0.2mol/L, and the amount ratio of described vanadium-containing compound and described reaction reagent is 0.5-10mmol: 0.1-2mmol.
4. method according to claim 3, it is characterized in that: in the preparation feedback step of described VOOH reactant, the time is 6 hours-12 hours; The concentration of the aqueous solution of described vanadium-containing compound is 0.01mol/L, and the amount ratio of described vanadium-containing compound and described reaction reagent is 1.5-3mmol: 0.5-1mmol.
5. a monoclinic phase VO who prepares doped with metallic element
2method, comprise the steps: the VOOH reactant doped with metallic element is reacted in containing the inert atmosphere of oxygen, obtain the monoclinic phase VO of described doped metallic elements after cooling
2; The volume percent of described oxygen in the described inert atmosphere that contains oxygen is 5-10%; Described metallic element is selected from least one in Mn, Ti, Cr, Mo and W;
In described reactions steps, temperature is 200-500 ℃, and the time is 1 minute-12 hours.
6. method according to claim 5, it is characterized in that: in described reactions steps, temperature is 400-450 ℃, the time is 1 minute-4 hours; Described inert atmosphere is nitrogen and/or argon gas atmosphere.
7. according to the described method of claim 5 or 6, it is characterized in that: described VOOH reactant is selected from least one in lepidocrocite, hollandite and montroseite;
The described reactant of the VOOH doped with metallic element is prepare by the following method and obtain:
Vanadium-containing compound and metal-salt are reacted with reaction solvent in water, reacted the complete described reactant of the VOOH doped with metallic element that obtains; Described reaction solvent is hydrazine hydrate aqueous solution; Described vanadium-containing compound is ammonium meta-vanadate; Described metal-salt is selected from the salt of following at least one metallic element: Mn, Ti, Cr, Mo and W; In the preparation feedback step of described VOOH reactant, temperature is 40 ℃-200 ℃, and the time is 30 minutes-48 hours; The concentration of the aqueous solution of described vanadium-containing compound is 0.001-0.2mol/L, and the amount ratio of described vanadium-containing compound, described metal-salt and described reaction reagent is 0.5-10mmol: 0.001-0.5mmol: 0.1-2mmol.
8. method according to claim 7, it is characterized in that: in the preparation feedback step of described VOOH reactant, temperature is 150-200 ℃, the time is 6 hours-12 hours; The concentration of the aqueous solution of described vanadium-containing compound is 0.01mol/L, and the amount ratio in described vanadium-containing compound, described metal-salt and described reaction reagent is 1.5-3mmol: 0.015-0.15mmol: 0.5-1mmol.
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| CN102757094B (en) * | 2011-04-28 | 2015-02-04 | 中国科学院上海硅酸盐研究所 | Method for preparing steady phase-A vanadium dioxide nanorod |
| CN102649583B (en) * | 2011-11-23 | 2014-07-09 | 中国科学技术大学 | Method for synthesizing monoclinic phase nano vanadium dioxide powder |
| CN102586796B (en) * | 2012-03-19 | 2015-06-03 | 中国科学院过程工程研究所 | Method for preparing vanadium dioxide powder through electrolysis |
| CN102674457A (en) * | 2012-06-15 | 2012-09-19 | 武汉大学 | Preparation method for vanadium trioxide doped powder material |
| CN102795668B (en) * | 2012-09-12 | 2014-07-09 | 西南大学 | Preparation method of VO2 |
| CN102826604A (en) * | 2012-09-26 | 2012-12-19 | 中国科学院上海硅酸盐研究所 | Preparation method of vanadium dioxide powder |
| CN104071843A (en) * | 2013-03-30 | 2014-10-01 | 中国科学院合肥物质科学研究院 | Preparation method of monodispersed M-phase vanadium dioxide nanoparticles |
| CN103928559A (en) * | 2014-04-11 | 2014-07-16 | 中国科学院合肥物质科学研究院 | Infrared detector and manufacturing method thereof |
| EP3197834A4 (en) | 2014-08-26 | 2018-05-02 | The Research Foundation for the State University of New York | Vo2 and v2o5 nano-and micro-materials and processes of making and uses of same |
| CN106012014A (en) * | 2016-06-06 | 2016-10-12 | 电子科技大学 | Vanadium dioxide film growing method |
| CN106698514B (en) * | 2016-12-27 | 2018-04-06 | 中国科学院合肥物质科学研究院 | The preparation method of P phase hypovanadic oxide nano-powders |
| CN112125338A (en) * | 2020-10-16 | 2020-12-25 | 成都先进金属材料产业技术研究院有限公司 | Method for preparing M-phase vanadium dioxide by solvothermal method |
| CN112209439B (en) * | 2020-10-16 | 2022-05-24 | 成都先进金属材料产业技术研究院有限公司 | Undoped low-temperature thermally-induced VO2Method for preparing powder material |
| CN114349042A (en) * | 2022-01-05 | 2022-04-15 | 中国科学技术大学 | Rutile phase doped metal oxide, stable defect-free rutile phase metal oxide and preparation method thereof |
| CN115323361B (en) * | 2022-07-12 | 2024-04-02 | 安徽建筑大学 | Nanometer flake VO that can change phase 2 Method for producing film |
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