CN108557886A - A kind of reaction kettle, a kind of vanadium dioxide nano powder and preparation method thereof - Google Patents
A kind of reaction kettle, a kind of vanadium dioxide nano powder and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of reaction kettles, a kind of vanadium dioxide nano powder and preparation method thereof.The method is completed using reaction kettle provided in an embodiment of the present invention, the method includes：The preparation of step 1, alkali formula vanadium oxide suspension；The preparation of step 2, vanadium dioxide nano powder first product；The preparation of step 3, vanadium dioxide nano powder.Special construction based on reaction kettle and it is volatilizable go out oxidizing gas oxidant use, so that hydro-thermal reaction carries out under a specific oxidizing atmosphere, the presence of specific oxidizing atmosphere, realize effective control of the pattern and performance to powder, required pattern and the hypovanadic oxide powder of performance is made by hydro-thermal reaction one-step method, which has the characteristics that easy to operate, of low cost.
Description
Technical field
The invention belongs to inorganic functional material fields, and in particular to a kind of reaction kettle, a kind of vanadium dioxide nano powder and
Preparation method.
Background technology
As science and technology continues to develop, requirement of the people to life comfort level is also continuously improved.The high temperature of summer keeps people past
Toward refrigerant environment is obtained by air-conditioning, the consumption of the energy is considerably increased.It has been reported that display, occupies and build in the energy consumption of Chinese air-conditioning
The 40~60% of energy consumption are built, and wherein 50% energy consumption is wasted by the window glass of building.Therefore using effective method come
The heat exchange of control window is of great significance.Vanadium dioxide (VO2) it is a kind of material with thermal induced phase transition property.Work as temperature
When degree is more than its phase transition temperature (68 DEG C), crystal structure is changed into Rutile Type (R) structure by monoclinic phase (M).In phase transformation
Meanwhile changing along with electrical and optical properties.It is semiconductor form before low temperature phase change, there is high saturating property near infrared light；
It is metallic state after high-temperature phase-change, the property reflected occurs to the light of near infrared band.The reversible multiple transformation of this characteristic energy, this
The reversible thermochromic properties of kind cause the research interest of researcher in world wide, and creatively according to this characteristic
Apply it to intelligent temperature control energy-saving glass field.When summer temperature is higher than phase transition temperature, VO2Film can be prevented effectively
Near infrared light with thermo-effect of infrared radiation is incident in building, is greatly slowed down indoor Wen Sheng and is disappeared to reduce the energy of air-conditioning
Consumption.And winter temperature it is relatively low when, VO2Film is again high to infrared light saturating, and near infrared light incidence interior is allowed to put forward high temperature rise.Therefore it makes
The VO of standby excellent properties2Film is of great significance to energy-saving and emission-reduction.
VO at present2Temperature control film includes mainly the vapor deposition methods such as magnetron sputtering, chemical vapor deposition, evaporation coating,
But these methods are there are preparation process complexity, instrument cost is higher, need to use the requirements such as particular substrate that it be caused not give birth in batches
Production.In addition, be directed to state of China, it is excessive and be difficult to realize all to change whole glass into glass cost with power saving function,
So if flexible VO can be prepared2Film then has huge applications foreground in the form of putting up to the transformation of existing building glass.
Prepare flexibility VO2The core of film is to prepare the VO with high quality2Nano-powder.Solid phase reaction method can be with
It is prepared on a large scale powder, but often particle is larger for its product, and grain size is not uniform enough and is difficult to meet actual demand.Liquid phase water
The method of heat prepares that nano-powder has many advantages, such as advantages of good crystallization, size is controllable and is widely used.But the VO that hydro-thermal is prepared2Powder
Body is often metastable monocline VO2(B), in order to make it be changed into the VO with phase-change characteristic2(M) powder generally requires
The high temperature anneal is carried out, and there is nano level powder higher surface energy to cause its often group of will produce in annealing process
It is poly-.Based on optical analog as a result, only working as VO2The size of powder can efficiently reduce the scattering of light when being less than 50nm.So grinding
Study carefully the VO that phase transition function is prepared using one step of hydrothermal method2(M) nano-powder come remove from Post isothermal treatment technique have it is important
Meaning.
Patent CN102120614A discloses a kind of method preparing hypovanadic oxide powder comprising using at alkaline reagent
The tetravalent vanadium ion aqueous solution of reason doping obtains the presoma treatment process of suspension, finally obtains VxM1-xO2Nano-powder,
Wherein M is the metals such as Sn, Bi, Ti, but has no that case study on implementation includes pure VO2(M) the direct preparation process of powder.Patent
CN105217684A, which is disclosed, a kind of preparing VO2The method of powder comprising be prepared for three using the method that carbon coating surface is modified
The particle that size is less than 100nm is tieed up, but its oversized limits application.Patent CN10164900A discloses a kind of utilize and mixes
One step of method of miscellaneous W is prepared for the VO of Rutile Type2(R) nano bar-shape powder, length dimension have also exceeded 50nm.
Therefore, how a step hydro-thermal prepares the VO of superfine M phases2Nano-powder is still this field difficulty urgently to be resolved hurrily
Topic.
Invention content
To solve the above problems, an embodiment of the present invention provides a kind of reaction kettle, including shell and liner, the liner are set
It sets in the shell；
The liner includes the first liner and the second liner；
Second liner is arranged in the chamber of first liner, the top end opening and bottom end envelope of second liner
Mouthful, height is less than the height of first liner, and is formed with accommodating space between first liner.
Optionally, the shell is stainless steel casing；
First liner is quartz lining, glass-lined or polytetrafluoroethyllining lining；
Second liner is quartz lining, glass-lined or polytetrafluoroethyllining lining.
The embodiment of the present invention additionally provides a kind of preparation method of vanadium dioxide nano powder, complete using above-mentioned reaction kettle
At, the method includes：
The preparation of step 1, alkali formula vanadium oxide suspension；
It using deionized water dissolving solid containing vanadium, obtains containing vanadium solution, be carried out to containing addition hydrazine hydrate solution in vanadium solution
Reaction, adds alkaline reagent, obtains the alkali formula vanadium oxide suspension after reaction；
The preparation of step 2, vanadium dioxide nano powder first product；
The alkali formula vanadium oxide suspension is centrifuged, alkali formula vanadium oxide solid is obtained, disperses the alkali formula using deionized water
Vanadium oxide solid, obtains precursor liquid, and the precursor liquid is transferred in the second liner of the reaction kettle, by second liner
It is added in the accommodating space for being placed in the chamber of first liner, and being formed to second liner with first liner
It is volatilizable go out oxidizing gas oxidant, first liner for the sealing for being built-in with second liner is positioned over described
Hydro-thermal reaction is carried out in the shell of reaction kettle, obtains the vanadium dioxide nano powder first product；
The preparation of step 3, vanadium dioxide nano powder；
After hydro-thermal reaction, the supernatant in second liner is removed, to the lower sediment in second liner
It cleaned, centrifuged and is dried, obtain the vanadium dioxide nano powder.
Optionally, it is described it is volatilizable go out oxidizing gas oxidant be aqueous hydrogen peroxide solution.
Optionally, described to use deionized water dissolving solid containing vanadium, it obtains containing vanadium solution, to containing addition hydration in vanadium solution
Hydrazine solution is reacted, and adds alkaline reagent after reaction, is obtained alkali formula vanadium oxide suspension and is included：
Using deionized water dissolving solid containing vanadium, obtain a concentration of 0.005~0.5mol/L contains vanadium solution；
Heating it is described containing vanadium solution to 35~85 DEG C, to heating after described in carry out containing hydrazine hydrate solution is added in vanadium solution
It reacts, hydrazine hydrate and the molar ratio containing vanadium ion in vanadium solution are 0.01 in the hydrazine hydrate solution:1~10:1；
Addition alkaline reagent carries out titration precipitation after reaction and pH is adjusted, and obtains the alkali formula vanadium oxide that pH is 5~12
Suspension.
Optionally, in the step 2, hydrogen peroxide rubs with vanadium ion in precursor liquid in the aqueous hydrogen peroxide solution
You are than being 0.001:1~5:1；
The reaction temperature of the hydro-thermal reaction is 200~260 DEG C, and the reaction time is for 24 hours~72h.
Optionally, after the centrifugation alkali formula vanadium oxide suspension, the method further includes：
Washing and again centrifugal treating are carried out to the alkali formula vanadium oxide solid after centrifugation using deionized water, obtain the alkali
Formula vanadium oxide solid.
Optionally, the solid containing vanadium includes at least one of vanadic sulfate, dichloro vanadyl and vanadic anhydride；
The alkaline reagent includes at least one of sodium hydroxide solution, ammonium hydroxide and potassium hydroxide solution.
The embodiment of the present invention additionally provides a kind of vanadium dioxide nano powder, and the vanadium dioxide nano powder is according to upper
What the method stated was prepared.
Optionally, when it is described it is volatilizable go out oxidizing gas oxidant be aqueous hydrogen peroxide solution, it is described contain vanadium solution
A concentration of 0.005~0.5mol/L, the hydrazine hydrate are 0.01 with the molar ratio containing vanadium ion in vanadium solution:1~10:1,
The alkali formula vanadium oxide suspension pH is 5~12, hydrogen peroxide and vanadium ion in precursor liquid in the aqueous hydrogen peroxide solution
Molar ratio is 0.001:1~5:1 and the hydro-thermal reaction reaction temperature be 200~260 DEG C, the reaction time be 6~72h
When, the vanadium dioxide nano powder is M phases, and is single crystal grain, and the single crystal grain has spherical structure or spherical knot
Structure, size are 20~50nm, and thermal induced phase transition point is adjustable as 0~70 DEG C.
Compared with prior art, the present invention includes following advantages：
The present invention provides a kind of reaction kettles, a kind of vanadium dioxide nano powder and preparation method thereof.The reaction kettle is
A kind of novel reaction kettle, including two liners of the first liner and the second liner, the second liner play buffer action, can be to second
The reaction solution that liner is interior and the second liner is different from addition in the accommodating space that the first liner is formed, uses reaction kettle to carry out hydro-thermal
When reaction, enters in another reaction solution after a certain reaction solution volatilization and react with another reaction solution, generate required product, pass through
Control the control of reactant ratio and reaction condition realization to product morphology, crystal structure.
A kind of preparation method of vanadium dioxide nano powder provided in an embodiment of the present invention, is carried using the embodiment of the present invention
What the reaction kettle of confession was completed, special construction based on reaction kettle and it is volatilizable go out oxidizing gas oxidant use so that
Hydro-thermal reaction carries out under a specific oxidizing atmosphere, and the presence of specific oxidizing atmosphere realizes the shape to powder
Required pattern and the hypovanadic oxide powder of performance has been made by hydro-thermal reaction one-step method, the system in effective control of looks and performance
Preparation Method has the characteristics that easy to operate, of low cost.
By the control to reaction reagent and reaction condition, the vanadium dioxide nano powder of M phases can be made, powder tool
There is single crystal grain, it is 20~60nm that single crystal grain, which has spherical structure or spherical structure, size, and thermal induced phase transition point is adjustable as
0~70 DEG C, which is a kind of thermochromism vanadium dioxide nano particle that size is minimum.
Description of the drawings
Fig. 1 is a kind of structural schematic diagram of reaction kettle provided in an embodiment of the present invention；
Fig. 2 is a kind of flow chart of the preparation method of vanadium dioxide nano provided in an embodiment of the present invention；
Fig. 3 is X-ray diffraction (XRD) figure of dry vanadium dioxide nano powder made from example 1；
Fig. 4 is dry vanadium dioxide nano scanning of materials electron microscope (SEM) figure made from example 1；
Fig. 5 is high resolution transmission electron microscopy (HRTEM) figure of dry vanadium dioxide nano particle made from example 1；
Fig. 6 is final product vanadium dioxide nano scanning of materials electron microscope (SEM) figure made from example 2.
Fig. 7 is final product vanadium dioxide nano scanning of materials electron microscope (SEM) figure made from example 3.
Fig. 8 is final product vanadium dioxide nano scanning of materials electron microscope (SEM) figure made from example 4.
Fig. 9 is final product vanadium dioxide nano scanning of materials electron microscope (SEM) figure made from example 5.
Figure 10 is final product vanadium dioxide nano scanning of materials electron microscope (SEM) figure made from example 6.
Figure 11 is final product vanadium dioxide nano scanning of materials electron microscope (SEM) figure made from example 7.
Specific implementation mode
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, below in conjunction with the accompanying drawings and specific real
Applying mode, the present invention is described in further detail.
Reaction kettle of the present invention, vanadium dioxide nano powder and preparation method thereof are carried out below by embodiment detailed
It describes in detail bright.
An embodiment of the present invention provides a kind of reaction kettle, reaction kettle includes shell and liner, reaction kettle using when liner put
It sets inside the shell, for the structure of liner as shown in Figure 1, liner includes the first liner 1 and the second liner 2, the first liner 1 includes first
Shell 11 and second shell 12, first shell 11 include side wall and bottom wall, and second shell 12 may include head cover, first shell 11
Sealed chamber can be formed with second shell 12.
Second liner 2 is arranged in the housing cavity of the first liner 1, the top end opening of the second liner 2 and bottom end is sealed, the
The height of two liners 2 is less than the body height of the first liner 1, and is formed with appearance between the second liner 2 and the shell of the first liner 1
Empty an A.
Reaction kettle provided in an embodiment of the present invention is a kind of novel reaction kettle, including the first liner and the second liner, two
A liner does not react with reaction solution, and the second liner plays buffer action, can be into the second liner and the second liner and the
Different reaction solutions is added in the accommodating space that one liner is formed, when carrying out hydro-thermal reaction using reaction kettle, a certain reaction solution is waved
Enter in another reaction solution after hair and react with another reaction solution, generate required product, by control reactant ratio and instead
Condition is answered to realize the control to product morphology.The reaction kettle is applicable to other hydro-thermal reactions such as oxygenating reaction and solvent heat is anti-
It answers, can be widely used.
Above-mentioned function based on reaction kettle, can be according to the material category of each structure of actual setting reaction kettle.For example, reaction
The shell of kettle can be stainless steel casing, and the first liner can be quartz lining, glass-lined, polytetrafluoroethyllining lining, stainless
Steel etc., the second liner can be quartz lining, glass-lined, polytetrafluoroethyllining lining, stainless steel etc..Except the liner of the example above
Outside material, every hyperbaric environment that can bear hydro-thermal reaction, the material for reaching seal request and not reacted with reaction solution.
It can be according to the size of each structure of actual setting reaction kettle, the structure ruler of every above-mentioned function suitable for reaction kettle
It is very little.For example, the second liner can be top end opening and the quartz ampoule that bottom end is sealed, specifically, when the volume of the first liner
For 50mL when, the outer diameter of the second liner, that is, quartz ampoule is 18~24mm, and the sidewall thickness of preferably 20~22mm, quartz ampoule are 1
The height of~3mm, preferably 1.5~2.5mm, quartz ampoule are 50~62mm, preferably 54~58mm.
The embodiment of the present invention additionally provides a kind of preparation method of vanadium dioxide nano powder, which is to use this
What the reaction kettle that inventive embodiments provide was completed.Fig. 2 is the preparation side of vanadium dioxide nano powder provided in an embodiment of the present invention
The flow chart of method, as shown in Fig. 2, the method includes：
The preparation of step 1, alkali formula vanadium oxide suspension.
It using deionized water dissolving solid containing vanadium, obtains containing vanadium solution, be carried out to containing addition hydrazine hydrate solution in vanadium solution
Reaction, adds alkaline reagent, obtains alkali formula vanadium oxide suspension after reaction.
It selects solid containing vanadium as vanadium source, using deionized water dissolving solid containing vanadium, obtains containing vanadium solution.Solid containing vanadium can
It, can be according to actually being selected, for example, solid containing vanadium may include vanadic sulfate, dichloro vanadyl and five oxidations there are many
At least one of two vanadium.
It prepares containing after vanadium solution, hydrazine hydrate solution is added in containing vanadium solution, the work of the hydrazine hydrate in hydrazine hydrate solution
On the one hand it is valence state protection to be provided to containing vanadium ion in vanadium solution, by the oxygen around vanadium ion as reducing agent with there is two aspects
Change reagent reduction, in case oxidising agent aoxidizes vanadium ion, while to carrying out also original place containing the vanadium ion aoxidized in vanadium solution
Reason, to ensure that the valence stability of vanadium ion, ensure that the property containing vanadium solution；On the other hand it is controlled as structure directing agent
Product pattern can be specifically coordinated with vanadium ion, to control product pattern.Experiment shows that suitable hydrazine hydrate can be with
Increase the Lacking oxygen in product, and then adjust transformation temperature, the pattern of product is controlled, such as adding suitable hydrazine hydrate can
There is spherical or spherical structure to control hypovanadic oxide powder, without adding or adding underexercise (such as additive amount is very few) hydration
Hydrazine can cause hypovanadic oxide powder to have sheet or the structures such as band-like.
Alkaline reagent provides hydroxide ion, for the vanadium ion in aqueous precipitating solution.By alkaline reagent be slowly added dropwise to
In solution containing vanadium solution and hydrazine hydrate solution after reaction, vanadium ion is made to be precipitated as alkali formula vanadium oxide.Alkaline reagent can
It, can be according to actually being selected, for example, alkaline reagent may include sodium hydroxide solution, ammonium hydroxide and hydroxide there are many
At least one of potassium solution.
The preparation of step 2, vanadium dioxide nano powder first product.
Alkali formula vanadium oxide suspension is centrifuged, alkali formula vanadium oxide solid is obtained, it is solid using deionized water dispersion alkali formula vanadium oxide
Body obtains precursor liquid, and precursor liquid is transferred in the second liner of reaction kettle, and the second liner is placed on to the chamber of the first liner
It is interior, and added in the accommodating space formed to the second liner and the first liner it is volatilizable go out oxidizing gas oxidant, will in
The first liner for being equipped with the sealing of the second liner is positioned in the shell of reaction kettle and carries out hydro-thermal reaction, obtains vanadium dioxide nano
Powder first product.
In hydrothermal reaction process, it is located at the oxidant in the accommodating space that the first liner and the second liner are formed as oxygenating
Agent can volatilize oxidizing gas, and oxidizing gas evaporates into the second liner, is given birth to hydro-thermal reaction under high-temperature and high-pressure conditions
At nanocrystal reacted, to obtain the hypovanadic oxide powder of required structure and performance.
When specific implementation, after centrifuging alkali formula vanadium oxide suspension, can also use deionized water to once centrifuging after
Alkali formula vanadium oxide solid carry out washing and centrifugal treating again, obtain the alkali formula vanadium oxide solid of surface cleaning.Wash number
It can be according to being actually configured with centrifugation number.
The preparation of step 3, vanadium dioxide nano powder.
After hydro-thermal reaction, the supernatant in the second liner is removed, the lower sediment in the second liner is cleaned,
Centrifugation and drying process, obtain vanadium dioxide nano powder.
After hydro-thermal reaction, the supernatant in the second liner is removed, to lower sediment, that is, titanium dioxide in the second liner
Vanadium nano-powder first product is post-processed, and is removed vanadium dioxide nano powder first product remained on surface substance, is obtained dry dioxy
Change vanadium nano-powder.
Post-processing may include cleaning, centrifugation, be dried, and according to actual setting wash number and can centrifuge number,
The parameters such as drying temperature and drying time are set.
Special construction based on reaction kettle and it is volatilizable go out oxidizing gas oxidant use so that hydro-thermal reaction exists
It carries out, the presence of specific oxidizing atmosphere, is realized to the pattern of powder and performance under one specific oxidizing atmosphere
Effectively control, has been made required pattern and the hypovanadic oxide powder of performance, which has by hydro-thermal reaction one-step method
The features such as easy to operate, of low cost.
It is volatilizable go out oxidizing gas oxidant be in hydrothermal reaction process it is volatilizable go out oxidizing gas oxidation
Agent, the oxidant can be it is a variety of, can be according to being actually configured.For example, it is volatilizable go out oxidizing gas oxidant can
Think aqueous hydrogen peroxide solution, in hydrothermal reaction process, aqueous hydrogen peroxide solution volatilizes hydrogen peroxide gas；For another example, may be used
The oxidant for volatilizing oxidizing gas can be potassium permanganate solid, and in hydrothermal reaction process, potassium permanganate volatilizes oxygen
Gas.
The reactant species and reaction condition of hydro-thermal reaction have an impact the structure and performance of product.
When the volume of the first liner of reaction kettle is 50mL, the second liner is the quartz ampoule that top end opening and bottom end are sealed,
The outer diameter of second liner, that is, quartz ampoule is 18~24mm, and the sidewall thickness of preferably 20~22mm, quartz ampoule are 1~3mm, preferably
Height for 1.5~2.5mm, quartz ampoule is 50~62mm, preferably 54~58mm, simultaneous selection aqueous hydrogen peroxide solution conduct
It is volatilizable go out oxidizing gas oxidant when, it is described to use deionized water dissolving solid containing vanadium, obtain containing vanadium solution, Xiang Han
Hydrazine hydrate solution is added in vanadium solution to be reacted, adds alkaline reagent after reaction, obtains alkali formula vanadium oxide suspension
Step may include：
Using deionized water dissolving solid containing vanadium, obtain containing vanadium solution, a concentration of 0.005~0.5mol/ containing vanadium solution
L, preferably 0.1~0.4mol/L, more preferably 0.2~0.3mol/L；Heating, to 35~85 DEG C, is preferably warming up to containing vanadium solution
40~70 DEG C, 50~65 DEG C are more preferably warming up to, is reacted, is hydrated containing addition hydrazine hydrate solution in vanadium solution to after heating
Hydrazine hydrate and the molar ratio containing vanadium ion in vanadium solution are 0.01 in hydrazine solution:1~10:1, preferably 0.2:1~2:1；Reaction
After add alkaline reagent carry out titration precipitation and pH adjust, obtain alkali formula vanadium oxide suspension, alkali formula vanadium oxide suspension
PH be 5~12, preferably pH be 8~11, more preferably 9~10.
Further, in step 2, disperse alkali formula vanadium oxide solid, the body of used deionized water using deionized water
Product is 5~20mL, preferably 5~15mL, more preferably 8~12mL.After accommodating space is added in hydrogenperoxide steam generator, to accommodating
Deionized water is added in space, the volume of deionized water is 3~10mL, preferably 4~8mL, more preferably 5~6mL.Peroxidating
The molar ratio of hydrogen peroxide and the vanadium ion in precursor liquid is 0.001 in aqueous solution of hydrogen:1~5:1, preferably 0.01:1~2:1；
The reaction temperature of hydro-thermal reaction is 200~260 DEG C, preferably 200~240 DEG C, more preferably 210~220 DEG C；Reaction time is
24~72h, preferably 30~50h, more preferably 40~48h.
By the selection of mentioned reagent and the control of reaction condition, vanadium dioxide nano powder obtained is M phases, powder and
For single crystal grain, single crystal grain has spherical structure or a spherical structure, and size is 20~50nm, and preferred size is 20~
40nm, more preferable size are 30~40nm, and thermal induced phase transition point is adjustable as 0~70 DEG C, preferably 30~65 DEG C, more preferably 40
~65 DEG C, which is a kind of thermochromism vanadium dioxide nano particle that size is minimum.By controlling vanadium ion in precursor liquid
The concentration of hydrogen peroxide in concentration of hydrazine hydrate, hydrogenperoxide steam generator in concentration, hydrazine hydrate solution, can adjust transformation temperature, will
Transformation temperature is adjusted near room temperature, therefore the preparation method has preferable application prospect, can prepare different transformation temperatures
Vanadium dioxide nano powder.
The embodiment of the present invention additionally provides a kind of vanadium dioxide nano powder, which is according to above-mentioned
Method be prepared.
When it is volatilizable go out oxidizing gas oxidant be aqueous hydrogen peroxide solution, containing vanadium solution a concentration of 0.005~
0.5mol/L, hydrazine hydrate are 0.01 with the molar ratio containing vanadium ion in vanadium solution:1~10:1, alkali formula vanadium oxide suspension
PH is 5~12, and the molar ratio of hydrogen peroxide and the vanadium ion in precursor liquid is 0.001 in aqueous hydrogen peroxide solution:1~5:1, with
And the reaction temperature of hydro-thermal reaction is 200~260 DEG C, when the reaction time is 24~72h, the vanadium dioxide nano powder of preparation is
M phases have single crystal grain, and it is 20~50nm that single crystal grain, which has spherical structure or spherical structure, size, and thermal induced phase transition point can
It is adjusted to 0~70 DEG C, which is a kind of thermochromism vanadium dioxide nano particle that size is minimum.
To make those skilled in the art more fully understand the present invention, below by way of specific embodiment to the titanium dioxide of the present invention
The preparation method of vanadium nano-powder is described in detail.
Following one or more tests are carried out to the vanadium dioxide nano powder prepared in following multiple embodiments：
(1) X-ray diffraction analysis
It is tested, is used using the Rigaku-D/max-2550pc type x-ray powder diffraction instruments of Hitachi, Japan
Cu-k α are as radiation source, wavelengthUsing Ni filter plates, Guan Liuwei 40mA, pipe pressure is 40KV, and scanning range is
10 °~90 °, sweep speed is 8 °/min, and step-length is 0.02 °；The vanadium dioxide nano material of the dry gained is put into load
It is flattened in slide, glass slide insertion instrument experiment slot center is tested；The identification of object phase and crystal structure information by
JADE5.0 softwares are analyzed.
(2) scanning electron microscope is observed
Micro- shape is carried out to vanadium dioxide nano material using Hitachi S-4800 high-resolution Flied emission scanning electron microscope (SEM)
Looks are tested.
(3) transmission electron microscope observation
Using F20S-twin types transmission electron microscope (TEM, FEI Tecnai G2)：Test VO2Nano-powder pattern
Feature and crystal structure.
Embodiment 1
The specific method for preparing vanadium dioxide nano powder may include：
(1) the vanadic sulfate powder of 0.55g is distributed in 20mL deionized waters, is placed in water-bath magnetic stirring apparatus and adds
Thermal agitation is dissolved, and heating temperature is 65 DEG C, and stirring 20min obtains the navy blue oxygen vanadium sulphate solution of clear.It takes a concentration of
The hydrazine hydrate aqueous solution 2.5mL of 1mol/L is slowly dropped in oxygen vanadium sulphate solution, obtains sky blue suspension.Slowly add later
Enter the sodium hydrate aqueous solution of a concentration of 1mol/L, adjusts pH to 10, obtain light brown alkali formula vanadium oxide suspension.
(2) to the light brown alkali formula vanadium oxide suspension of gained carry out centrifugal treating, obtain alkali formula vanadium oxide, using go from
Sub- water is cleaned by ultrasonic alkali formula vanadium oxide, and the alkali formula vanadium oxide after cleaning is distributed in 10mL deionized waters, agitated uniform
After be transferred in quartz lining (the second liner), the outer diameter of the quartz lining is 22mm, thickness 2mm, is highly 58mm.
It is that 30% aqueous hydrogen peroxide solution is distributed in 6mL deionized waters to take 0.1mL mass fractions, is transferred into poly-
In tetrafluoroethene liner (the first liner).Quartz lining equipped with alkali formula vanadium oxide suspension is transferred to containing aquae hydrogenii dioxidi
In the polytetrafluoroethyllining lining of solution, it is anti-that polytetrafluoroethyllining lining is placed on to progress hydro-thermal in the shell of stainless steel cauldron
It answers, in electric heating bellows after 220 DEG C of heat preservation 48h, obtains black precipitate, upper layer is colourless transparent liquid, and hydro-thermal reaction is completed.
(3) supernatant liquor in quartz lining in reaction kettle is removed, obtains black precipitate, using deionized water, anhydrous
Ethyl alcohol, isopropanol clean black precipitate successively, and centrifugal treating and drying process are carried out to the black precipitate after cleaning,
In, centrifugal rotational speed when centrifugal treating is 12500r/min, and the drying temperature of vacuum drying chamber is 60 DEG C when drying process, dry
Time is for 24 hours, to obtain vanadium dioxide nano powder desciccate.
The powder prepared after hydro-thermal reaction in the present invention is M phase powders, is not necessarily to subsequent heat treatment, and the present invention is anti-to hydro-thermal
Drying powder after answering is tested, as a result as follows：By Fig. 3 of XRD test gained it is found that the hypovanadic oxide powder prepared is M
Phase structure.By Fig. 4 of SEM test gained it is found that the hypovanadic oxide powder prepared is spherical or spherical structure, grain size is more equal
One, and size is respectively less than 50nm.By Fig. 5 of HRTEM test gained it is found that the hypovanadic oxide powder prepared is mono-crystalline structures, and
Size is about 30nm.
Embodiment 2
The specific method for preparing vanadium dioxide nano powder may include：
(1) the dichloro oxygen vanadium powder body of 0.464g is distributed in 20mL deionized waters, is placed in water-bath magnetic stirring apparatus
Heating stirring dissolves, and obtains suspension, and heating temperature is 65 DEG C, and stirring 20min obtains the navy blue vanadic sulfate of clear
Solution.It is added without hydrazine hydrate solution, is directly slowly added to the sodium hydrate aqueous solution of a concentration of 1mol/L, pH to 10 is adjusted, obtains
To light brown alkali formula vanadium oxide suspension.
(2) to the light brown alkali formula vanadium oxide suspension of gained carry out centrifugal treating, obtain alkali formula vanadium oxide, using go from
Sub- water is cleaned by ultrasonic alkali formula vanadium oxide, and the alkali formula vanadium oxide after cleaning is distributed in 10mL deionized waters, agitated uniform
After be transferred in quartz lining (the second liner), the outer diameter of the quartz lining is 22mm, thickness 2mm, is highly 58mm.
It is added without aqueous hydrogen peroxide solution, 6mL deionized waters are directly added to polytetrafluoroethyllining lining (the first liner)
It is interior.Quartz lining equipped with alkali formula vanadium oxide suspension is transferred to the polytetrafluoroethyllining lining containing aqueous hydrogen peroxide solution
In, polytetrafluoroethyllining lining is placed in the shell of stainless steel cauldron and carries out hydro-thermal reaction, 220 DEG C in electric heating bellows
After keeping the temperature 48h, black precipitate is obtained, upper layer is colourless transparent liquid, and hydro-thermal reaction is completed.
(3) supernatant liquor in quartz lining in reaction kettle is removed, obtains black precipitate, using deionized water, anhydrous
Ethyl alcohol, isopropanol clean black precipitate successively, and centrifugal treating and drying process are carried out to the black precipitate after cleaning,
In, centrifugal rotational speed when centrifugal treating is 12500r/min, and the drying temperature of vacuum drying chamber is 60 DEG C when drying process, dry
Time is for 24 hours, to obtain vanadium dioxide nano powder desciccate.By Fig. 6 of SEM test gained it is found that the powder generated is band
Shape pattern, only contains a small amount of little particle powder, and reason is：It does not participate in reacting as the hydrazine hydrate of structure directing agent, powder
Pattern be tend to be band-like based on.
Embodiment 3
The specific method for preparing vanadium dioxide nano powder may include：
(1) the vanadic anhydride powder of 0.3g is distributed in 20mL deionized waters, is placed in water-bath magnetic stirring apparatus
Heating stirring obtains suspension, and heating temperature is 65 DEG C, and the hydrazine hydrate aqueous solution and 6.7mL of a concentration of 1mol/L of 1mL is added
The dilute hydrochloric acid solution of a concentration of 1mol/L stirs the navy blue oxygen vanadium sulphate solution of acquisition clear after 20min.It takes a concentration of
The hydrazine hydrate aqueous solution 2.5mL of 1mol/L is slowly dropped in oxygen vanadium sulphate solution, obtains sky blue suspension.Slowly add later
Enter the sodium hydrate aqueous solution of a concentration of 1mol/L, adjusts pH to 10, obtain light brown alkali formula vanadium oxide suspension.
(2) to the light brown alkali formula vanadium oxide suspension of gained carry out centrifugal treating, obtain alkali formula vanadium oxide, using go from
Sub- water is cleaned by ultrasonic alkali formula vanadium oxide, and the alkali formula vanadium oxide after cleaning is distributed in 10mL deionized waters, agitated uniform
After be transferred in quartz lining (the second liner), the outer diameter of the quartz lining is 22mm, thickness 2mm, is highly 58mm.
It is that 30% aqueous hydrogen peroxide solution is distributed in 6mL deionized waters to take 1mL mass fractions, is transferred into poly- four
In vinyl fluoride liner (the first liner).Quartz lining equipped with alkali formula vanadium oxide suspension is transferred to water-soluble containing hydrogen peroxide
In the polytetrafluoroethyllining lining of liquid, polytetrafluoroethyllining lining is placed in the shell of stainless steel cauldron and carries out hydro-thermal reaction,
In electric heating bellows after 220 DEG C of heat preservation 48h, black precipitate is obtained, upper layer is colourless transparent liquid, and hydro-thermal reaction is completed.
(3) supernatant liquor in quartz lining in reaction kettle is removed, obtains black precipitate, using deionized water, anhydrous
Ethyl alcohol, isopropanol clean black precipitate successively, and centrifugal treating and drying process are carried out to the black precipitate after cleaning,
In, centrifugal rotational speed when centrifugal treating is 12500r/min, and the drying temperature of vacuum drying chamber is 60 DEG C when drying process, dry
Time is for 24 hours, to obtain vanadium dioxide nano powder desciccate.By Fig. 7 of SEM test gained it is found that the powder generated is band
Shape pattern, reason are：Excessive hydrogen peroxide and hydration hydrazine reaction, cause hydrazine hydrate to lose the effect of structure directing agent, and lead
Cause the generation of high-valence state barium oxide or vanadium oxygen hydrate.
Embodiment 4
The specific method for preparing vanadium dioxide nano powder may include：
(1) the vanadic sulfate powder of 0.2g is distributed in 20mL deionized waters, is placed in water-bath magnetic stirring apparatus and adds
Thermal agitation is dissolved, and heating temperature is 65 DEG C, and stirring 20min obtains the navy blue oxygen vanadium sulphate solution of clear.It takes a concentration of
The hydrazine hydrate aqueous solution 2.5mL of 1mol/L is slowly dropped in oxygen vanadium sulphate solution, obtains sky blue suspension.Slowly add later
Enter the sodium hydrate aqueous solution of a concentration of 1mol/L, adjusts pH to 10, obtain light brown alkali formula vanadium oxide suspension.
(2) to the light brown alkali formula vanadium oxide suspension of gained carry out centrifugal treating, obtain alkali formula vanadium oxide, using go from
Sub- water is cleaned by ultrasonic alkali formula vanadium oxide, and the alkali formula vanadium oxide after cleaning is distributed in 10mL deionized waters, agitated uniform
After be transferred in quartz lining (the second liner), the outer diameter of the quartz lining is 22mm, thickness 2mm, is highly 58mm.
It is that 30% aqueous hydrogen peroxide solution is distributed in 6mL deionized waters to take 0.1mL mass fractions, is transferred into poly-
In tetrafluoroethene liner (the first liner).Quartz lining equipped with alkali formula vanadium oxide suspension is transferred to containing aquae hydrogenii dioxidi
In the polytetrafluoroethyllining lining of solution, it is anti-that polytetrafluoroethyllining lining is placed on to progress hydro-thermal in the shell of stainless steel cauldron
It answers, in electric heating bellows after 220 DEG C of heat preservation 48h, obtains black precipitate, upper layer is colourless transparent liquid, and hydro-thermal reaction is completed.
(3) supernatant liquor in quartz lining in reaction kettle is removed, obtains black precipitate, using deionized water, anhydrous
Ethyl alcohol, isopropanol clean black precipitate successively, and centrifugal treating and drying process are carried out to the black precipitate after cleaning,
In, centrifugal rotational speed when centrifugal treating is 12500r/min, and the drying temperature of vacuum drying chamber is 60 DEG C when drying process, dry
Time is for 24 hours, to obtain vanadium dioxide nano powder desciccate.By Fig. 8 of SEM test gained it is found that the powder generated includes
Band-like and two kinds of patterns of graininess, reason are：Compared to the content of hydrazine hydrate and hydrogen peroxide, vanadium ion concentration is very few, causes
Most of hydrazine hydrate is cleaned out during alkali formula vanadium oxide cleans, and compared to remaining hydrazine hydrate, content of hydrogen peroxide is inclined
It is more, cause part powder peroxidating, powder and rodlike the phenomenon that coexisting occurs.
Embodiment 5
The specific method for preparing vanadium dioxide nano powder may include：
(1) the vanadic sulfate powder of 0.978g is distributed in 20mL deionized waters, is placed in water-bath magnetic stirring apparatus
Heating stirring dissolves, and heating temperature is 50 DEG C, and stirring 20min obtains the navy blue oxygen vanadium sulphate solution of clear.Take concentration
It is slowly dropped in oxygen vanadium sulphate solution for the hydrazine hydrate aqueous solution 5mL of 1mol/L, obtains sky blue suspension.Slowly add later
Enter the sodium hydrate aqueous solution of a concentration of 1mol/L, adjusts pH to 9, obtain light brown alkali formula vanadium oxide suspension.
(2) to the light brown alkali formula vanadium oxide suspension of gained carry out centrifugal treating, obtain alkali formula vanadium oxide, using go from
Sub- water is cleaned by ultrasonic alkali formula vanadium oxide, and the alkali formula vanadium oxide after cleaning is distributed in 10mL deionized waters, agitated uniform
After be transferred in quartz lining (the second liner), the outer diameter of the quartz lining is 22mm, thickness 2mm, is highly 58mm.
It is that 30% aqueous hydrogen peroxide solution is distributed in 6mL deionized waters to take 0.05mL mass fractions, is transferred into
In polytetrafluoroethyllining lining (the first liner).Quartz lining equipped with alkali formula vanadium oxide suspension is transferred to containing hydrogen peroxide
In the polytetrafluoroethyllining lining of aqueous solution, it is anti-that polytetrafluoroethyllining lining is placed on to progress hydro-thermal in the shell of stainless steel cauldron
It answers, in electric heating bellows after 210 DEG C of heat preservation 40h, obtains black precipitate, upper layer is colourless transparent liquid, and hydro-thermal reaction is completed.
(3) supernatant liquor in quartz lining in reaction kettle is removed, obtains black precipitate, using deionized water, anhydrous
Ethyl alcohol, isopropanol clean black precipitate successively, and centrifugal treating and drying process are carried out to the black precipitate after cleaning,
In, centrifugal rotational speed when centrifugal treating is 12500r/min, and the drying temperature of vacuum drying chamber is 60 DEG C when drying process, dry
Time is for 24 hours, to obtain vanadium dioxide nano powder desciccate.By Fig. 9 of SEM test gained it is found that the vanadium dioxide prepared
Powder is spherical or spherical structure, and grain size is more uniform, and size is respectively less than 50nm.
Embodiment 6
The specific method for preparing vanadium dioxide nano powder may include：
(1) the vanadic sulfate powder of 0.6g is distributed in 20mL deionized waters, is placed in water-bath magnetic stirring apparatus and adds
Thermal agitation is dissolved, and heating temperature is 35 DEG C, and stirring 20min obtains the navy blue oxygen vanadium sulphate solution of clear.Take 2.5mL dense
Degree is that the hydrazine hydrate aqueous solution of 1mol/L is slowly dropped in oxygen vanadium sulphate solution, obtains sky blue suspension.Slowly add later
Enter the potassium hydroxide aqueous solution of a concentration of 1mol/L, adjust pH to 12, obtains light brown alkali formula vanadium oxide suspension.
(2) centrifugal treating is carried out to the light brown alkali formula vanadium oxide suspension of gained, obtains alkali formula vanadium oxide precipitation, uses
Deionized water is cleaned by ultrasonic alkali formula vanadium oxide, and the alkali formula vanadium oxide after cleaning is re-dispersed into 20mL deionized water solutions
In, it is agitated uniformly after be transferred in the second polytetrafluoroethyllining lining (the second liner), the outer diameter of liner is 24mm, and thickness is
1mm is highly 62mm.
The aqueous hydrogen peroxide solution that 0.2mL mass fractions are 30% is distributed in 5mL deionized waters, is transferred into the
In one polytetrafluoroethyllining lining (the first liner), the second polytetrafluoroethyllining lining equipped with alkali formula vanadium oxide suspension is transferred to
In the first polytetrafluoroethyllining lining containing aqueous hydrogen peroxide solution, the first polytetrafluoroethyllining lining is placed on stainless steel reaction
In the shell of kettle, hydro-thermal reaction is carried out, in electric heating bellows after 200 DEG C of heat preservations for 24 hours, obtains black precipitate, upper layer is colourless
Transparency liquid, hydro-thermal reaction are completed.
(3) supernatant liquor in quartz lining in reaction kettle is removed, obtains black precipitate, using deionized water, anhydrous
Ethyl alcohol, isopropanol clean black precipitate successively, and centrifugal treating and drying process are carried out to the black precipitate after cleaning,
In, centrifugal rotational speed when centrifugal treating is 12500r/min, and the drying temperature of vacuum drying chamber is 60 DEG C when drying process, dry
Time is for 24 hours, to obtain spherical nano vanadium dioxide nano-powder.As shown in Figure 10, the nano vanadium dioxide powder of preparation
In, in addition to including spherical nano vanadium dioxide powder, also it is mingled with part laminated structure, reason is：It is relatively low bath temperature, anti-
It answers temperature to influence the interaction of hydrazine hydrate and alkali formula vanadyl, leads to the structure-directing effect unobvious of hydrazine hydrate.
Embodiment 7
The specific method for preparing vanadium dioxide nano powder may include：
(1) the vanadic sulfate powder of 0.5g is distributed in 20mL deionized waters, is placed in water-bath magnetic stirring apparatus and adds
Thermal agitation is dissolved, and heating temperature is 85 DEG C, and stirring 20min obtains the navy blue oxygen vanadium sulphate solution of clear.Take 2.5mL dense
Degree is that the hydrazine hydrate aqueous solution of 1mol/L is slowly dropped in oxygen vanadium sulphate solution, obtains sky blue suspension.Slowly add later
Enter the sodium hydrate aqueous solution of a concentration of 1mol/L, adjust pH to 5, obtains light brown alkali formula vanadium oxide suspension.
(2) centrifugal treating is carried out to the light brown alkali formula vanadium oxide suspension of gained, obtains alkali formula vanadium oxide precipitation, uses
Deionized water is cleaned by ultrasonic alkali formula vanadium oxide, and the alkali formula vanadium oxide after cleaning is re-dispersed into 5mL deionized water solutions,
It is agitated uniformly after be transferred in the second polytetrafluoroethyllining lining (the second liner), the outer diameter of liner is 18mm, and thickness is
3mm is highly 50mm.
The aqueous hydrogen peroxide solution that 0.1mL mass fractions are 30% is distributed in 10mL deionized waters, is transferred into
In first polytetrafluoroethyllining lining (the first liner), it will be shifted equipped with the second polytetrafluoroethyllining lining of alkali formula vanadium oxide suspension
To in the first polytetrafluoroethyllining lining containing aqueous hydrogen peroxide solution, it is anti-that the first polytetrafluoroethyllining lining is placed on stainless steel
In the shell for answering kettle, hydro-thermal reaction is carried out, in electric heating bellows after 260 DEG C of heat preservation 72h, obtains black precipitate, upper layer is nothing
Color transparency liquid, hydro-thermal reaction are completed.
(3) supernatant liquor in quartz lining in reaction kettle is removed, obtains black precipitate, using deionized water, anhydrous
Ethyl alcohol, isopropanol clean black precipitate successively, and centrifugal treating and drying process are carried out to the black precipitate after cleaning,
In, centrifugal rotational speed when centrifugal treating is 12500r/min, and the drying temperature of vacuum drying chamber is 60 DEG C when drying process, dry
Time is for 24 hours, to obtain spherical nano vanadium dioxide nano-powder.As shown in figure 11, the nano vanadium dioxide powder of preparation
In, in addition to including spherical nano vanadium dioxide powder, also it is mingled with part club shaped structure, reason is：Excessively high temperature promotes
Hydrogen peroxide quickly aoxidizes powder, cause part powder formed high-valence state stick sheet barium oxide or vanadium oxygen hydrate.
The present invention provides a kind of reaction kettles, a kind of vanadium dioxide nano powder and preparation method thereof.The reaction kettle is
A kind of novel reaction kettle, including two liners of the first liner and the second liner, the second liner play buffer action, can be to second
The reaction solution that liner is interior and the second liner is different from addition in the accommodating space that the first liner is formed, uses reaction kettle to carry out hydro-thermal
When reaction, enters in another reaction solution after a certain reaction solution volatilization and react with another reaction solution, generate required product, pass through
Control the control of reactant ratio and reaction condition realization to product morphology.
A kind of preparation method of vanadium dioxide nano powder provided in an embodiment of the present invention, is carried using the embodiment of the present invention
What the reaction kettle of confession was completed, special construction based on reaction kettle and it is volatilizable go out oxidizing gas oxidant use so that
Hydro-thermal reaction carries out under a specific oxidizing atmosphere, and the presence of specific oxidizing atmosphere realizes the shape to powder
Required pattern and the hypovanadic oxide powder of performance has been made by hydro-thermal reaction one-step method, the system in effective control of looks and performance
Preparation Method has the characteristics that easy to operate, of low cost.
By the control to reaction reagent and reaction condition, the vanadium dioxide nano powder of M phases can be made, powder tool
There is single crystal grain, it is 20~60nm that single crystal grain, which has spherical structure or spherical structure, size, and thermal induced phase transition point is adjustable as
0~70 DEG C, which is a kind of thermochromism vanadium dioxide nano particle that size is minimum.
Above to the preparation method and one kind of a kind of reaction kettle provided by the present invention, a kind of vanadium dioxide nano powder
Vanadium dioxide nano powder is described in detail, specific case used herein to the principle of the present invention and embodiment into
Elaboration is gone, the explanation of above example is only intended to facilitate the understanding of the method and its core concept of the invention；Meanwhile for this
The those skilled in the art in field, according to the thought of the present invention, there will be changes in the specific implementation manner and application range,
In conclusion the content of the present specification should not be construed as limiting the invention.
Claims (10)
1. a kind of reaction kettle, which is characterized in that including shell and liner, the liner is arranged in the shell；
The liner includes the first liner and the second liner；
Second liner is arranged in the chamber of first liner, the top end opening of second liner and bottom end is sealed,
Its height is less than the height of first liner, and is formed with accommodating space between first liner.
2. reaction kettle according to claim 1, which is characterized in that the shell is stainless steel casing；
First liner is quartz lining, glass-lined or polytetrafluoroethyllining lining；
Second liner is quartz lining, glass-lined or polytetrafluoroethyllining lining.
3. a kind of preparation method of vanadium dioxide nano powder, which is characterized in that anti-using claim 1-2 any one of them
Kettle is answered to complete, the method includes：
The preparation of step 1, alkali formula vanadium oxide suspension；
It using deionized water dissolving solid containing vanadium, obtains containing vanadium solution, be reacted to containing addition hydrazine hydrate solution in vanadium solution,
Alkaline reagent is added after reaction, obtains the alkali formula vanadium oxide suspension；
The preparation of step 2, vanadium dioxide nano powder first product；
The alkali formula vanadium oxide suspension is centrifuged, alkali formula vanadium oxide solid is obtained, disperseing the alkali formula using deionized water aoxidizes
Vanadium solid, obtains precursor liquid, and the precursor liquid is transferred in the second liner of the reaction kettle, and second liner is placed
In the chamber of first liner, and addition can wave in the accommodating space formed to second liner with first liner
First liner for the sealing for being built-in with second liner is positioned over the reaction by the oxidant for sending out oxidizing gas
Hydro-thermal reaction is carried out in the shell of kettle, obtains the vanadium dioxide nano powder first product；
The preparation of step 3, vanadium dioxide nano powder；
After hydro-thermal reaction, the supernatant in second liner is removed, the lower sediment in second liner is carried out
Cleaning, centrifugation and drying process, obtain the vanadium dioxide nano powder.
4. according to the method described in claim 3, it is characterized in that, it is described it is volatilizable go out oxidizing gas oxidant be peroxide
Change aqueous solution of hydrogen.
5. according to the method described in claim 4, it is characterized in that, the use deionized water dissolving solid containing vanadium, is contained
Vanadium solution is reacted to containing addition hydrazine hydrate solution in vanadium solution, adds alkaline reagent after reaction, obtains the oxidation of alkali formula
Vanadium suspension includes：
Using deionized water dissolving solid containing vanadium, obtain a concentration of 0.005~0.5mol/L contains vanadium solution；
Heating it is described containing vanadium solution to 35~85 DEG C, to heating after described in containing be added in vanadium solution hydrazine hydrate solution carry out it is anti-
It answers, hydrazine hydrate and the molar ratio containing vanadium ion in vanadium solution are 0.01 in the hydrazine hydrate solution:1~10:1；
Addition alkaline reagent carries out titration precipitation after reaction and pH is adjusted, and it is suspended to obtain the alkali formula vanadium oxide that pH is 5~12
Liquid.
6. according to the method described in claim 5, it is characterized in that, in the step 2, mistake in the aqueous hydrogen peroxide solution
The molar ratio of hydrogen oxide and the vanadium ion in precursor liquid is 0.001:1~5:1；
The reaction temperature of the hydro-thermal reaction is 200~260 DEG C, and the reaction time is for 24 hours~72h.
7. according to the method described in claim 3, it is characterized in that, after the centrifugation alkali formula vanadium oxide suspension, institute
The method of stating further includes：
Washing and again centrifugal treating are carried out to the alkali formula vanadium oxide solid after centrifugation using deionized water, obtain the alkali formula oxygen
Change vanadium solid.
8. according to the method described in claim 3, it is characterized in that, the solid containing vanadium include vanadic sulfate, dichloro vanadyl and
At least one of vanadic anhydride；
The alkaline reagent includes at least one of sodium hydroxide solution, ammonium hydroxide and potassium hydroxide solution.
9. a kind of vanadium dioxide nano powder, which is characterized in that the vanadium dioxide nano powder is appointed according to claim 3-8
What the method described in one was prepared.
10. vanadium dioxide nano powder according to claim 9, which is characterized in that when it is described it is volatilizable go out oxidisability gas
The oxidant of body is aqueous hydrogen peroxide solution, a concentration of 0.005~0.5mol/L containing vanadium solution, in the hydrazine hydrate solution
Hydrazine hydrate is 0.01 with the molar ratio containing vanadium ion in vanadium solution:1~10:1, the alkali formula vanadium oxide suspension pH are 5
~12, the molar ratio of hydrogen peroxide and vanadium ion in precursor liquid is 0.001 in the aqueous hydrogen peroxide solution:1~5:1, and
The reaction temperature of the hydro-thermal reaction is 200~260 DEG C, and when the reaction time is 6~72h, the vanadium dioxide nano powder is M
Phase, and be single crystal grain, it is 20~50nm, thermal induced phase transition that the single crystal grain, which has spherical structure or spherical structure, size,
Point is adjustable as 0~70 DEG C.
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| CN110203972A (en) * | 2019-06-13 | 2019-09-06 | 湖北大学 | The preparation method of phase-M vanadium dioxide nanometre powder |
| CN112919539A (en) * | 2021-03-25 | 2021-06-08 | 北京理工大学 | Tungsten-niobium co-doped vanadium dioxide powder and preparation method thereof |
| CN113511678A (en) * | 2020-04-09 | 2021-10-19 | 北京理工大学 | M-phase vanadium dioxide nano powder and preparation method and preparation device thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1721054A (en) * | 2004-07-16 | 2006-01-18 | 中国科学院大连化学物理研究所 | The autoclave of the controlled interpolation reactant of original position |
| CN105753050A (en) * | 2014-12-18 | 2016-07-13 | 刘闽苏 | A preparing method of rutile vanadium dioxide nanometer particles and the particles |
| CN206424911U (en) * | 2017-01-23 | 2017-08-22 | 太原科技大学 | A kind of hydrothermal synthesis reaction device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1721054A (en) * | 2004-07-16 | 2006-01-18 | 中国科学院大连化学物理研究所 | The autoclave of the controlled interpolation reactant of original position |
| CN1309464C (en) * | 2004-07-16 | 2007-04-11 | 中国科学院大连化学物理研究所 | High-pressure reaction still capable of realizing in-situ controllable charging of reactants |
| CN105753050A (en) * | 2014-12-18 | 2016-07-13 | 刘闽苏 | A preparing method of rutile vanadium dioxide nanometer particles and the particles |
| CN206424911U (en) * | 2017-01-23 | 2017-08-22 | 太原科技大学 | A kind of hydrothermal synthesis reaction device |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110203972A (en) * | 2019-06-13 | 2019-09-06 | 湖北大学 | The preparation method of phase-M vanadium dioxide nanometre powder |
| CN113511678A (en) * | 2020-04-09 | 2021-10-19 | 北京理工大学 | M-phase vanadium dioxide nano powder and preparation method and preparation device thereof |
| CN112919539A (en) * | 2021-03-25 | 2021-06-08 | 北京理工大学 | Tungsten-niobium co-doped vanadium dioxide powder and preparation method thereof |
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