CN101880060A - Method for quickly preparing monoclinic phase VO2 - Google Patents
Method for quickly preparing monoclinic phase VO2 Download PDFInfo
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- CN101880060A CN101880060A CN 201010231179 CN201010231179A CN101880060A CN 101880060 A CN101880060 A CN 101880060A CN 201010231179 CN201010231179 CN 201010231179 CN 201010231179 A CN201010231179 A CN 201010231179A CN 101880060 A CN101880060 A CN 101880060A
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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 monocline phase and cubic rutile phase hypovanadic oxide powder, especially relate to a kind of quick preparation monocline phase VO
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 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(abbreviate VO as
2(M)) with cubic rutile VO mutually
2(abbreviate VO as
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 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) the more common method of preparation realizes (＞12 hours) for long term annealing under the vapor deposition apparatus of logical hydrogen or inert atmosphere.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 (VO
2(M) and VO
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 preparation monocline phase VO
2Method.
A kind of preparation monocline phase VO provided by the invention
2Method, comprise the steps: that metastable phase is contained the vanadium reactant reacts in inert atmosphere, obtain described monocline phase VO after the cooling
2
In the 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 was preferably 1 minute-4 hours, and more preferably 1 minute-30 minutes, especially preferred 1 minute; Described inert atmosphere is nitrogen and/or argon gas atmosphere; Described metastable phase contains the vanadium reactant and is selected from the metastable phase vanadium dioxide and (is abbreviated as VO
2(B)), A phase VO
2(be abbreviated as VO
2(A)), paramontroseite (is abbreviated as VO
2(P) or VO
2And VO (paramontroseite))
2.H
2At least a among the O.This reaction is annealing reaction, and used annealing device can be sectional type tube furnace or a common gaseous phase deposition stove commonly used in this area.
Preparation provided by the invention is doped with the monocline phase VO of metallic element
2Method, comprise the steps: that the metastable phase that will be doped with metallic element contains the vanadium reactant and reacts in inert atmosphere, obtain the monocline phase VO of described doped metallic elements after the cooling
2
Described metallic element is selected from least a among Mn, Ti, Cr, Mo and the W;
In the 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 was preferably 1 minute-4 hours, more preferably 1 minute; Reaction pressure is a normal pressure; Described inert atmosphere is nitrogen and/or argon gas atmosphere; Described metastable phase contains the vanadium reactant and is selected from metastable phase vanadium dioxide, A phase VO
2, paramontroseite and VO
2.H
2At least a among the O; This reaction is annealing reaction, and used annealing device can be sectional type tube furnace or a common gaseous phase deposition stove commonly used in this area.
Another kind of preparation monocline phase VO provided by the invention
2Method, comprise the steps: the VOOH reactant is reacted in containing the inert atmosphere of oxygen, obtain described monocline phase VO after the cooling
2
In the described reactions steps, temperature is 200-500 ℃, and the time is 1 minute-12 hours.
In the reactions steps of this method, temperature is 200-500 ℃, and preferred 400-450 ℃, more preferably 400 ℃, the time was preferably 1 minute-4 hours, more preferably 0.5 hour-6 hours, and especially preferred 0.5 hour; Reaction pressure is a 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 a in hollandite (being abbreviated as VOOH (H) or Hollandite VOOH) and the montroseite (being abbreviated as VOOH (M) or Montroseite VOOH); This reaction is annealing reaction, and used annealing device can be sectional type tube furnace or a common gaseous phase deposition stove commonly used in this area.
Preparation provided by the invention is doped with the monocline phase VO of metallic element
2Method, comprise the steps: that the VOOH reactant that will be doped with metallic element reacts in containing the inert atmosphere of oxygen, obtain the monocline phase VO of described doped metallic elements after the cooling
2
Described metallic element is selected from least a among Mn, Ti, Cr, Mo and the W;
In the described reactions steps, temperature is 200-500 ℃, and the time is 1 minute-12 hours.
In the described reactions steps of this method, temperature is preferably 400-450 ℃, and more preferably 400 ℃, the time was preferably 1 minute-4 hours, more preferably 30 minutes; Reaction pressure is a 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%, preferred 5%; Described VOOH reactant is selected from least a in lepidocrocite, hollandite and the montroseite.This reaction is annealing reaction, and used annealing device can be sectional type tube furnace or a common gaseous phase deposition stove commonly used in this area.
Among four kinds of preparation methods that the invention described above provides, described metastable phase vanadium-containing compound can get according to various ordinary method preparations, as being prepared as follows: the aqueous solution and the reaction reagent of vanadium-containing compound are reacted, and reaction finishes and obtains described metastable phase vanadium dioxide; Described reaction reagent is selected from least a 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 the 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
3At least a with in the methyl ethyl diketone vanadium complex; In the described reactions steps, temperature is 40 ℃-220 ℃, and preferred 150-200 ℃, the time is 30 minutes-48 hours, and the time was 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 the amount ratio of acid or alkali is 0.5-10mmol: 0.1-2.5mmol in described vanadium-containing compound and the described reaction reagent, preferred 1.5-3mmol: 0.5-1mmol.This reaction is hydro-thermal reaction, and used hydro-thermal reaction device can be a various industrial stainless steel still reaction unit commonly used in this area, as hydro-thermal autoclave or glass reflux.
The described metastable phase vanadium-containing compound that is doped with metallic element can get according to various ordinary method preparations, as being prepared as follows: vanadium-containing compound and metal-salt are reacted with reaction solvent in water, and reaction finishes and obtains the described metastable phase vanadium dioxide that is doped with metallic element; Wherein, described reaction reagent is selected from least a 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 the 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
3At least a with in the methyl ethyl diketone vanadium complex; Described metal-salt is selected from the salt of following at least a metallic element: Mn, Ti, Cr, Mo and W; In the described reactions steps, temperature is 40 ℃-200 ℃, and preferred 150-200 ℃, the time is 30 minutes-48 hours, and the time was 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, the amount ratio of acid or alkali is 0.5-10mmol: 0.001-0.5mmol: 0.1-2mmol in described vanadium-containing compound, described metal-salt and the described reaction reagent, preferred 1.5-3mmol: 0.015-0.15mmol: 0.5-1mmol.This reaction is hydro-thermal reaction, and used hydro-thermal reaction device can be a various industrial stainless steel still reaction unit commonly used in this area, as hydro-thermal autoclave or glass reflux.
Described VOOH reactant can get according to various ordinary method preparations, and as being prepared as follows: the aqueous solution and the reaction reagent of vanadium-containing compound are reacted, and reaction finishes and obtains described VOOH reactant; Described reaction reagent is selected from least a 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 the 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
2At least a with in the methyl ethyl diketone vanadium complex; In the described reactions steps, temperature is 40 ℃-200 ℃, and preferred 40-200 ℃, the time is 30 minutes-48 hours, and the time was 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 the amount ratio of acid or alkali is 0.5-10mmol: 0.1-2mmol in described vanadium-containing compound and the described reaction reagent, preferred 1.5-3mmol: 0.5-1mmol.This reaction is hydro-thermal reaction, and used hydro-thermal reaction device can be a various industrial stainless steel still reaction unit commonly used in this area, as hydro-thermal autoclave or glass reflux.
The described VOOH reactant that is doped with metallic element can get according to various ordinary method preparations, as being prepared as follows: vanadium-containing compound and metal-salt are reacted with reaction solvent in water, and reaction finishes and obtains the described VOOH reactant that is doped with metallic element; Wherein, described reaction reagent is selected from least a 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 the 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
3At least a with in the methyl ethyl diketone vanadium complex; Described metal-salt is selected from the salt of following at least a metallic element: Mn, Ti, Cr, Mo and W;
In the described reactions steps, temperature is 40 ℃-200 ℃, and preferred 40-200 ℃, the time is 30 minutes-48 hours, and the time was 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 the amount ratio of acid or alkali is 0.5-10mmol: 0.1-2mmol in described vanadium-containing compound and the described reaction reagent, preferred 1.5-3mmol: 0.5-1mmol.This reaction is hydro-thermal reaction, and used hydro-thermal reaction device can be a various industrial stainless steel still reaction unit commonly used in this area, as hydro-thermal autoclave or glass reflux.
Among above-mentioned four kinds of preparation methods, described A phase VO
2(A) can be according to the preparation of following method and get: at volume be adding 2mmol VO (acac) in the tetrafluoroethylene reactor of 50ml
2With 40mL distilled water, and with mass percentage concentration be 10% HCOOH aqueous solution 1mmol to regulate pH value be 3～4, stir 30min after, seal in the still shell of packing into, the back is at 220 ℃ of maintenance 12h down, centrifugal collection product behind the naturally cooling obtains A phase VO
2(A).
Described metastable phase VO
2(B) can be according to the preparation of following method and get: at volume be adding 2mmol V in the tetrafluoroethylene reactor of 50mL
2O
5With 40mL distilled water, and with mass percentage concentration be 10% HCOOH aqueous solution 1mmol to regulate pH value be 3～4, stir 30min after, seal in the still shell of packing into, 200 ℃ of maintenances 12 hours down, behind the naturally cooling, centrifugal collection product obtains metastable phase VO then
2(B).
Described VO
2(P) (paramontroseite) can be according to the preparation of following method and get: at volume be adding 4mmol Na in the tetrafluoroethylene reactor of 50ml
3VO
412H
2O, 20mmol TAA (thioacetamide) and 50ml distilled water behind the stirring 30min, in the still shell of packing into, keep 12h down at 200 ℃ then, and behind the naturally cooling, centrifugal collection product obtains above-mentioned VO
2(P) (paramontroseite).
Described VOOH (L) can be according to the preparation of following method and get: at volume is adding 2mmol metavanadic acid ammonia and 35ml distilled water in the tetrafluoroethylene reactor of 50ml, back adding 8ml mass percentage concentration is 10% ammoniacal liquor, after stirring 30min, pack into and seal in the still shell, the back keeps 12h down at 200 ℃, behind the naturally cooling, centrifugal collection product obtains described VOOH (L).
Described VOOH (H) can be according to the preparation of following method and get: at volume is adding 2mmol metavanadic acid ammonia and 35ml distilled water in the tetrafluoroethylene reactor of 50ml, the back adds 1ml 1M HCl dissolves it fully, back adding 3ml mass percentage concentration is 10% hydrazine hydrate aqueous solution, and centrifugal collection obtains V (OH) behind the stirring 30min
2NH
2The back is itself and 1mmol NH
4F mixes and to be placed in the polytetrafluoroethylliner liner that 35ml distilled water is housed, after pack into and seal in the still shell, keep 12h down at 200 ℃, behind the naturally cooling, centrifugal collection product obtains described VOOH (H).
Described VOOH (M) can be according to the preparation of following method and get: at volume is adding 2mmol sodium orthovanadate, 2mmol thioacetamide, 0.5mmol NH in the tetrafluoroethylene reactor of 50ml
4F and 35ml distilled water seal in the still shell of packing into behind the stirring 30min, keep 12h down at 200 ℃, and behind the naturally cooling, centrifugal collection product obtains described VOOH (M).
The preparation monocline phase VO that the invention described above provides
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 monocline phase VO after cooling into
2(VO
2(M)), and the VOOH reactant is mixing under the inert atmosphere that an amount of oxygen is arranged, and oxidation and inversion of phases take place simultaneously, and is attended by deviating from of water, finally changes VO after the cooling into
2(M).
Preparation monocline phase VO provided by the invention
2With the monocline that is doped with metallic element VO mutually
2Method, can be under the normal pressure inert atmosphere protection, metastable phase vanadium dioxide or new thing phase VOOH are converted into monocline phase VO fast
2This method technology is simple, cost is low, productive rate is high, purity is good, and can prepare the hypovanadic oxide powder (VO of intelligent power saving performance in enormous quantities fast
2(M) phase), the atom transformation efficiency is 100% (being that vanadium atom in each precursor can both be converted into the vanadium atom in the product fully).This monocline phase VO
2The metal-insulator phase transition temperature be 20 ℃～68 ℃.The various monocline phase VO that are 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, this method has the following advantages:
1, suitable vanadium of the present invention source is wider, can prepare very high metastable phase vanadium dioxide precursor of purity and VOOH precursor, the precursor VO that the gained high purity has intelligent power saving character after annealing through hydro-thermal reaction
2(M).
2,, the shortlyest can realize that metastable phase vanadium dioxide precursor is to having intelligent power saving character VO at one minute because to the suitable selection of precursor, annealing time shortens greatly than traditional annealing time among the present invention
2(M) quick conversion has been shortened the reaction times greatly, has reduced the consumption of the energy, and lays a good foundation for a large amount of suitability for industrialized production, has wide industrial prospect.
3, the monocline 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 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.
Description of drawings
Fig. 1 is gained paramontroseite VO among the embodiment 3
2(P) XRD figure spectrum.
Fig. 2 is the XRD figure spectrum of embodiment 11 preparation gained montroseites (Montroseite VOOH).
Fig. 3 is the XRD figure spectrum of the hollandite (Hollandite VOOH) of gained among the embodiment 9.
Fig. 4 is embodiment 3 preparation gained monocline phase VO
2(M) XRD figure spectrum.
Fig. 5 is embodiment 3 preparation gained monocline phase VO
2(M) DSC circulation collection of illustrative plates.
Embodiment
The invention will be further described below in conjunction with specific embodiment, but the present invention is not limited to following examples.Method is ordinary method if no special instructions described in the following embodiment.Described conversion unit is conventional equipment if no special instructions.
Embodiment 1: use VO
2(B) preparation VO
2(M)
1) be to add 2mmol V in the tetrafluoroethylene reactor of 50mL at volume
2O
5With 40mL distilled water, and be that to regulate the pH value be 3～4 for 10% the HCOOH aqueous solution with mass percentage concentration.After stirring 30min, seal in the still shell of packing into, kept 12 hours down at 200 ℃ then, behind the naturally cooling, centrifugal collection product obtains VO
2(B).
2) will fill 0.5g VO
2(B) porcelain boat places and is connected with N
2Tube furnace in, and at 450 ℃ of following annealing 12h, obtain purity after the cooling and be 100% VO
2(M).The XRD spectra of this compound and DSC circulation collection of illustrative plates and Fig. 4 and no substantive difference shown in Figure 5.As seen from the figure, this compound structure is correct.
Embodiment 2: with A phase VO
2(A) preparation VO
2(M)
1) be to add 2mmol VO (acac) in the tetrafluoroethylene reactor of 50ml at volume
2(methyl ethyl diketone vanadyl title complex) and 40mL distilled water, and with mass percentage concentration be 10% the HCOOH aqueous solution to regulate pH value be 3～4, behind the stirring 30min, pack into and seal in the still shell, the back keeps 12h down at 220 ℃, and centrifugal collection product behind the naturally cooling obtains A phase VO
2(A).
2) will fill 0.5g VO
2(A) porcelain boat places and is connected with N
2Tube furnace in, and at 450 ℃ of following annealing 12h, obtain purity after the cooling and be 100% VO
2(M).The XRD spectra of this compound and DSC circulation collection of illustrative plates and Fig. 4 and no substantive difference shown in Figure 5.As seen from the figure, this compound structure is correct.
Embodiment 3: use VO
2(P) preparation VO
2(M)
1) be to add 4mmol Na in the tetrafluoroethylene reactor of 50ml at volume
3VO
412H
2O (sodium orthovanadate), 20mmol TAA (thioacetamide) and 50ml distilled water behind the stirring 30min, in the still shell of packing into, keep 12h down at 200 ℃ then, and behind the naturally cooling, centrifugal collection product obtains 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 places and is connected with N
2Tube furnace in, and 400 ℃ of down annealing 1 minute, obtain purity after the cooling and be 100% VO
2(M).This compound VO
2(M) XRD spectra and DSC circulation collection of illustrative plates are respectively Fig. 4 and shown in Figure 5.As seen from the figure, this compound structure is correct.
Embodiment 4: with the VO that mixes Mo
2(B) preparation VO
2(M)
1) be to add 2mmol V in the tetrafluoroethylene reactor of 50ml at volume
2O
5, 0.25mmol Na
2MoO
4With 4mmol H
2C
2O
42H
2O, the back adds 40ml distilled water, stir 30min after, seal in the still shell of packing into, the back keeps 24h down at 200 ℃, behind the naturally cooling, centrifugal collection product obtains mixing the VO of Mo
2(B).
2) will fill the VO that 0.5g mixes Mo
2(B) porcelain boat places and is connected with N
2Tube furnace in and under 450 ℃, annealing 12h obtains purity and is 100% the VO that mixes Mo after the cooling
2(M).The XRD spectra of this compound and DSC circulation collection of illustrative plates and Fig. 4 and no substantive difference shown in Figure 5.As seen from the figure, this compound structure is correct.
Embodiment 5: with the VO that mixes W
2(B) preparation VO
2(M)
1) be to add 2mmol V in the tetrafluoroethylene reactor of 50ml at volume
2O
5, 0.25mmol Na
2WO
4With 4mmol H
2C
2O
42H
2O, the back adds 40ml distilled water, stir 30min after, seal in the still shell of packing into, the back keeps 24h down at 200 ℃, behind the naturally cooling, centrifugal collection product obtains mixing the VO of W
2(B).
2) will fill the VO that 0.5g mixes W
2(B) porcelain boat places and is connected with N
2Tube furnace in, and at 450 ℃ of following annealing 12h, obtain purity after the cooling and be 100% the VO that mixes W
2(M).The XRD spectra of this compound and DSC circulation collection of illustrative plates and Fig. 4 and no substantive difference shown in Figure 5.As seen from the figure, this compound structure is correct.
Embodiment 6: with the VO that mixes Ti
2(B) preparation VO
2(M)
1) be to add 2mmol V in the tetrafluoroethylene reactor of 50ml at volume
2O
5, 0.25mmolK
2TiO (C
2O
4)
2With 4mmol H
2C
2O
42H
2O, the back adds 40ml distilled water, stir 30min after, seal in the still shell of packing into, the back keeps 24h down at 200 ℃, behind the naturally cooling, centrifugal collection product obtains mixing the VO of Ti
2(B).
2) will fill the VO that 0.5g mixes Ti
2(B) porcelain boat places and is connected with N
2Tube furnace in, and at 450 ℃ of following annealing 12h, obtain purity after the cooling and be 100% the VO that mixes Ti
2(M).The XRD spectra of this compound and DSC circulation collection of illustrative plates and Fig. 4 and no substantive difference shown in Figure 5.As seen from the figure, this compound structure is correct.
Embodiment 7: with the VO that mixes Mn
2(B) preparation VO
2(M)
1) be to add 2mmol V in the tetrafluoroethylene reactor of 50ml at volume
2O
5, 0.25mmol MnCO
3With 4mmol H
2C
2O
42H
2O, the back adds 40ml distilled water, stir 30min after, seal in the still shell of packing into, the back keeps 24h down at 200 ℃, behind the naturally cooling, centrifugal collection product obtains mixing the VO of Mn
2(B).
2) will fill the VO that 0.5g mixes Mn
2(B) porcelain boat places and is connected with N
2Tube furnace in, and at 450 ℃ of following annealing 12h, obtain purity after the cooling and be 100% the VO that mixes Mn
2(M).The XRD spectra of this compound and DSC circulation collection of illustrative plates and Fig. 4 and no substantive difference shown in Figure 5.As seen from the figure, this compound structure is correct.
Embodiment 8: with VOOH (L) preparation VO
2(M)
1) be to add 2mmol metavanadic acid ammonia and 35ml distilled water in the tetrafluoroethylene reactor of 50ml at volume, back adding 8ml mass percentage concentration is 10% ammoniacal liquor, after stirring 30min, pack into and seal in the still shell, the back keeps 12h down at 200 ℃, behind the naturally cooling, centrifugal collection product obtains VOOH (L).
2) porcelain boat that will fill 0.5g VOOH (L) places the tube furnace that is connected with oxygen and nitrogen mixture (wherein the volume percent of oxygen is 5%), and at 400 ℃ of annealing 6h down, obtains purity after the cooling and be 100% VO
2(M).The XRD spectra of this compound and DSC circulation collection of illustrative plates and Fig. 4 and no substantive difference shown in Figure 5.As seen from the figure, this compound structure is correct.
Embodiment 9: prepare VO with Hollandite VOOH
2(M)
1) be to add 2mmol metavanadic acid ammonia and 35ml distilled water in the tetrafluoroethylene reactor of 50ml at volume, the back adds 1ml 1M HCl dissolves it fully, back adding 3ml mass percentage concentration is 10% hydrazine hydrate aqueous solution, and centrifugal collection obtains V (OH) behind the stirring 30min
2NH
2Then with gained V (OH)
2NH
2With 1mmol NH
4The F mixing is placed in the polytetrafluoroethylliner liner that 35ml distilled water is housed, and seals in the still shell of packing into, keeps 12h down at 200 ℃, and behind the naturally cooling, centrifugal collection product obtains Hollandite VOOH.The XRD figure spectrum of this compound as shown in Figure 3.As seen from the figure, this compound structure is correct.
2) porcelain boat that will fill 0.5g Hollandite VOOH places the tube furnace that is connected with oxygen and nitrogen mixture (wherein the volume percent of oxygen is 5%), and at 400 ℃ of annealing 30min down, obtains purity after the cooling and be 100% VO
2(M).The XRD figure spectrum of this compound does not have substantive difference with Fig. 2.As seen from the figure, this compound structure is correct.
Embodiment 10: prepare VO with the Hollandite VOOH that mixes tungsten
2(M)
1) be to add 2mmol metavanadic acid ammonia and 35ml distilled water in the tetrafluoroethylene reactor of 50ml at volume, the back adds 1ml 1M HCl dissolves it fully, add the 3ml mass percentage concentration again and be 10% hydrazine hydrate aqueous solution, stir 30min after centrifugal collection obtain V (OH)
2NH
2After, with V (OH)
2NH
2With 1mmol NH
4F and 0.1mmol sodium wolframate mix and are placed in the polytetrafluoroethylliner liner that 35ml distilled water is housed, and seal in the still shell of packing into, keep 12h down at 200 ℃, and behind the naturally cooling, centrifugal collection product obtains being doped with the Hollandite VOOH of tungsten.This compound XRD figure spectrum do not have substantive difference with Fig. 3.As seen from the figure, this compound structure is correct.
2) will fill the porcelain boat that 0.5g is doped with the Hollandite VOOH of tungsten and place the tube furnace that is connected with oxygen and nitrogen mixture (wherein the volume percent of oxygen is 5%), and, obtain purity after the cooling and be 100% the VO that is doped with tungsten at 400 ℃ of following annealing 30min
2(M).The XRD figure spectrum of this compound does not have substantive difference with Fig. 2.As seen from the figure, this compound structure is correct.
Embodiment 11: prepare VO with Montroseite VOOH
2(M)
1) be to add 2mmol sodium orthovanadate, 2mmol thioacetamide, 0.5mmol NH in the tetrafluoroethylene reactor of 50ml at volume
4F and 35ml distilled water seal in the still shell of packing into behind the stirring 30min, keep 12h down at 200 ℃, and behind the naturally cooling, centrifugal collection product obtains Montroseite VOOH.
2) porcelain boat that will fill 0.5g Montroseite VOOH places the tube furnace that is connected with oxygen and nitrogen mixture (wherein the volume percent of oxygen is 5%), and at 400 ℃ of annealing 30min down, obtains purity after the cooling and be 100% VO
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 that 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 that scope of the present invention is by claims and be equal to and limit to these embodiment.
Claims (8)
1. one kind prepares monocline phase VO
2Method, comprise the steps: that metastable phase is contained the vanadium reactant reacts in inert atmosphere, obtain described monocline phase VO after the cooling
2
In the described reactions steps, temperature is 200-500 ℃, and the time is 1 minute-12 hours.
2. method according to claim 1 is characterized in that: in the described reactions steps, temperature is 400-450 ℃, and the time is 1 minute-4 hours; Described inert atmosphere is nitrogen and/or argon gas atmosphere; Described metastable phase contains the vanadium reactant and is selected from metastable phase vanadium dioxide, A phase VO
2, paramontroseite and VO
2.H
2At least a among the O;
It is get according to comprising the steps method preparation that described metastable phase contains the vanadium reactant: the aqueous solution and the reaction reagent of vanadium-containing compound are reacted, and reacting finishes obtains described metastable phase and contains the vanadium reactant;
Described reaction reagent is selected from least a 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 the aqueous sodium hydroxide solution; 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
3At least a with in the methyl ethyl diketone vanadium complex; In the described reactions steps, temperature is 40 ℃-220 ℃, and preferred 150-200 ℃, the time is 30 minutes-48 hours, and the time was 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 the amount ratio of acid or alkali is 0.5-10mmol: 0.1-2.5mmol in described vanadium-containing compound and the described reaction reagent, preferred 1.5-3mmol: 0.5-1mmol.
3. one kind prepares the monocline phase VO that is doped with metallic element
2Method, comprise the steps: that the metastable phase that will be doped with metallic element contains the vanadium reactant and reacts in inert atmosphere, obtain the monocline phase VO of described doped metallic elements after the cooling
2
Described metallic element is selected from least a among Mn, Ti, Cr, Mo and the W; In the described reactions steps, temperature is 200-500 ℃, and the time is 1 minute-12 hours.
4. method according to claim 3 is characterized in that: in the described reactions steps, temperature is 40 ℃-200 ℃, and preferred 150-200 ℃, the time is 30 minutes-48 hours, preferred 6 hours-12 hours; Described inert atmosphere is nitrogen and/or argon gas atmosphere; Described metastable phase contains the vanadium reactant and is selected from metastable phase vanadium dioxide, A phase VO
2, paramontroseite and VO
2.H
2At least a among the O;
It is according to the preparation of following method and get that the described metastable phase that is doped with metallic element contains the vanadium reactant: vanadium-containing compound and metal-salt are reacted with reaction reagent in water, reacting finishes obtain described be doped with metallic element contain the vanadium reactant; Described reaction reagent is selected from least a 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 the aqueous sodium hydroxide solution; 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
3At least a with in the methyl ethyl diketone vanadium complex; Described metal-salt is selected from the salt of following at least a metallic element: Mn, Ti, Cr, Mo and W; In the described reactions steps, temperature is 40 ℃-200 ℃, and preferred 150-200 ℃, the time is 30 minutes-48 hours, and the time was 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, the amount ratio of acid or alkali is 0.5-10mmol: 0.001-0.5mmol: 0.1-2mmol in described vanadium-containing compound, described metal-salt and the described reaction reagent, preferred 1.5-3mmol: 0.015-0.15mmol: 0.5-1mmol.
5. one kind prepares monocline phase VO
2Method, comprise the steps: the VOOH reactant is reacted in containing the inert atmosphere of oxygen, obtain described monocline phase VO after the cooling
2
In the described reactions steps, temperature is 200-500 ℃, and the time is 1 minute-12 hours.
6. method according to claim 5 is characterized in that: in the described reactions steps, temperature is 400-450 ℃, and the time is 1 minute-4 hours; 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 is selected from least a in lepidocrocite, hollandite and the montroseite;
Described VOOH reactant is to get according to comprising the steps the method preparation: the aqueous solution and the reaction reagent of vanadium-containing compound are reacted, and reaction finishes and obtains described VOOH reactant; Described reaction reagent is selected from least a 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 the aqueous sodium hydroxide solution; 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
2At least a with in the methyl ethyl diketone vanadium complex; In the described reactions steps, temperature is 40 ℃-200 ℃, and preferred 40-200 ℃, the time is 30 minutes-48 hours, and the time was 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 the amount ratio of acid or alkali is 0.5-10mmol: 0.1-2mmol in described vanadium-containing compound and the described reaction reagent, preferred 1.5-3mmol: 0.5-1mmol.
7. one kind prepares the monocline phase VO that is doped with metallic element
2Method, comprise the steps: that the VOOH reactant that will be doped with metallic element reacts in containing the inert atmosphere of oxygen, obtain the monocline phase VO of described doped metallic elements after the cooling
2
Described metallic element is selected from least a among Mn, Ti, Cr, Mo and the W;
In the described reactions steps, temperature is 200-500 ℃, and the time is 1 minute-12 hours.
8. method according to claim 7 is characterized in that: in the described reactions steps, temperature is 400-450 ℃, and the time is 1 minute-4 hours; 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 is selected from least a in lepidocrocite, hollandite and the montroseite;
The described VOOH reactant that is doped with metallic element is to get according to following method preparation:
Vanadium-containing compound and metal-salt are reacted with reaction solvent in water, and reaction finishes and obtains the described VOOH reactant that is doped with metallic element; Described reaction reagent is selected from least a 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 the aqueous sodium hydroxide solution; 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
3At least a with in the methyl ethyl diketone vanadium complex; Described metal-salt is selected from the salt of following at least a metallic element: Mn, Ti, Cr, Mo and W; In the described reactions steps, temperature is 40 ℃-200 ℃, and preferred 150-200 ℃, the time is 30 minutes-48 hours, preferred 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, the amount ratio of acid or alkali is 0.5-10mmol: 0.001-0.5mmol: 0.1-2mmol in described vanadium-containing compound, described metal-salt and the described reaction reagent, preferred 1.5-3mmol: 0.015-0.15mmol: 0.5-1mmol.
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