CN109319838A - A kind of preparation method of rutile phase hypovanadic oxide ultra-fine nano-powder - Google Patents
A kind of preparation method of rutile phase hypovanadic oxide ultra-fine nano-powder Download PDFInfo
- Publication number
- CN109319838A CN109319838A CN201811407464.9A CN201811407464A CN109319838A CN 109319838 A CN109319838 A CN 109319838A CN 201811407464 A CN201811407464 A CN 201811407464A CN 109319838 A CN109319838 A CN 109319838A
- Authority
- CN
- China
- Prior art keywords
- powder
- rutile phase
- suspension
- hypovanadic oxide
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention discloses a kind of preparation methods of rutile phase hypovanadic oxide ultra-fine nano-powder, comprising the following steps: S1, ammonium hydroxide and acid tetravalence vanadium solution fast reaction obtain suspension B；S2, it is sealed insulated and stirred processing to the suspension B, obtains colloid suspension C, and the holding temperature is not higher than the boiling point of solvent in tetravalence vanadium solution；S3, colloid suspension C is separated by solid-liquid separation and is cleaned, obtain hydrated hydroxide vanadyl colloid D；S4, hydrated hydroxide vanadyl colloid D is dried, and is sintered in protective atmosphere, obtain rutile phase hypovanadic oxide ultra-fine nano-powder.The rutile phase hypovanadic oxide particle purity that process of the invention is prepared is high, and size is smaller and uniform, and favorable dispersibility, is the outstanding raw material that high quality Vanadium dioxide intelligent temperature control applies window.
Description
Technical field
The invention belongs to metal-insulator phase transition technical field of material chemistry, and in particular to a kind of rutile phase hypovanadic oxide is super
The preparation method of thin nano-powder.
Background technique
The energy problem got worse and environmental pollution are at a global critical issue.Clean energy resource and Novel ring
The demand of energy-saving material is protected just in rapid growth.The temperature controlling instruments such as wherein building energy consumption, especially air-conditioning, heating, according to statistics
30% or so of total energy consumption is accounted for.The study found that in building or vehicle glass surface coating, it can be in inflammation
Hot summer day part reflective thermal radiation (10-50%, according to material therefor different from), to reduce the use of indoor air-conditioning system
And energy consumption.However, many energy-saving material production technologies are complicated so far, and it is at high cost, it is seriously polluted in production process, thus simultaneously
It is unsuitable for large-scale commercially use, energy-saving and environment-friendly effect can not be reached.
Building glass energy conservation becomes focus.The glass film energy-saving material for being indicated in space in a newspaper at present and being applied in market, such as
The intelligent temperature controls coatings such as electrochromism, photochromic, thermochromism and gas-discoloration, adjusting optical band is largely focused on can
It is light-exposed, it is bad to infrared light (heat source) band results, and certain additional illumination is caused to pay.On the other hand, wave is inhaled in part
Material such as lanthanum hexaboride, tin-antiomony oxide, tin oxide fluorine etc. possesses good near-infrared barrier property.Regrettably, these materials
The barrier to infrared light can not intelligently be regulated and controled, hot (infrared ray) is obstructed in winter instead and enter the room, to have to consume
More energy (heating), and the preparation cost of such material is higher, is not easy to large area use.
Vanadium dioxide is a kind of ideal function phase-change material, and the phase transition temperature (68 DEG C) of nearly room temperature is especially doped
Phase transition temperature can be down to room temperature (20-30 DEG C) by part transition element (such as tungsten, molybdenum, niobium etc.), become research the most extensive
One of phase-change material.It is metallic state that this material, which is higher than under phase transition temperature, can reflect near infrared band light (heat accumulation light area)；
And lower than being insulation posture or semiconductor under phase transition temperature, then light can be allowed freely to penetrate.Other intelligent glass are different from,
The transmitance of visible light is changed without the change according to temperature.So far, vanadium dioxide material be considered as it is a kind of more
Ideal intelligent temperature control material.Especially barium oxide is global rich reserves, cheap natural minerals, as vanadium oxide
Source material makes it possible to be mass produced and apply.
The preparation method research of rutile phase hypovanadic oxide nano particle is more at present, including traditional hydro-thermal reaction
Method, solvent thermal reaction method, microemulsion method and solid reaction process.Wherein, solvent heat and microemulsion liquid reaction method are needed using certain
Organic solvent as reaction medium, higher cost, and part organic solvent, there are certain toxicity and other safeties are hidden
Suffer from.The reaction pressure of hydro-thermal reaction method is higher, causes the initial investment using the method in terms of equipment and production safety higher.
The reaction system of hydro-thermal reaction is also relative complex, and the shipwreck as solvent will lead to some additional waste water to recycle
Processing cost.Solid reaction process can generate some exhaust gas in the synthesis of vanadium dioxide nano particle, will lead to some exhaust gas
Processing cost, and the particle homogeneity formed is larger, and production energy consumption is higher.
Summary of the invention
It is super the technical problem to be solved by the present invention is to provide a kind of rutile phase hypovanadic oxide for the above-mentioned prior art
The preparation method of thin nano-powder.
The technical problem to be solved by the present invention is to for the above-mentioned prior art provide it is a kind of at low cost, easy to operate and
And particle size is small and particle size is controllable, the preparation side of the rutile phase hypovanadic oxide ultra-fine nano-powder of good dispersion
Method.
The present invention solves the above problems used technical solution are as follows: a kind of rutile phase hypovanadic oxide ultra-fine nano-powder
Preparation method, comprising the following steps:
S1, ammonium hydroxide and acid tetravalence vanadium solution A fast reaction, obtain suspension B；
S2, it is sealed insulated and stirred processing to the suspension B, obtains colloid suspension C, and the holding temperature is not higher than
The boiling point of solvent in tetravalence vanadium solution；
S3, colloid suspension C is separated by solid-liquid separation and is cleaned, obtain hydrated hydroxide vanadyl colloid D；
S4, hydrated hydroxide vanadyl colloid D is dried, and is sintered in protective atmosphere, obtain Rutile Type titanium dioxide
Vanadium ultra-fine nano-powder.
Preferably, the preparation method of the rutile phase hypovanadic oxide ultra-fine nano-powder, step S1 specifically: past
Ammonium hydroxide is added in tetravalence vanadium solution A, stirs to get suspension B；Wherein, the vanadium ion concentration in the tetravalence vanadium solution A is
0.1-2mol/L is dissolved in water by tetravalence vanadic salts and obtains.
Preferably, the preparation method of the rutile phase hypovanadic oxide ultra-fine nano-powder, step S2 specifically: will
Suspension B, which is placed in closed container, persistently stirs and is heated to 20-100 DEG C, keeps the temperature and stirs, and obtains colloid suspension C.
Preferably, the preparation method of the rutile phase hypovanadic oxide ultra-fine nano-powder, the tetravalence vanadium solution
For vanadic sulfate, vanadyl oxalate, divanadyl tetrachloride, ascorbic acid vanadyl, citric acid vanadyl or tartaric acid vanadyl it is one or more,
It include either tetravalence vanadium made of vanadic anhydride, ammonium metavanadate or sodium vanadate are restored by reducing agent by the compound of vanadium
Salting liquid.
Preferably, the preparation method of the rutile phase hypovanadic oxide ultra-fine nano-powder, in step S1, ammonium hydroxide
Additional amount is, so that ammonium hydroxide content is the 1-30% of suspension quality in the suspension B.
Preferably, the preparation method of the rutile phase hypovanadic oxide ultra-fine nano-powder, in the step S1,
Into tetravalence vanadium solution A be added ammonium hydroxide before, add doped chemical into the tetravalence vanadium solution A, be specially tungsten, molybdenum, magnesium,
Any one or more in titanium, iron, niobium, zirconium and fluorine.
7, the preparation method of rutile phase hypovanadic oxide ultra-fine nano-powder as described in claim 1, which is characterized in that
In step S3, described be separated by solid-liquid separation uses centrifugal process, sedimentation or membrane filter method；In cleaning step, using water, first
Alcohol, ethyl alcohol or isopropanol are as cleaning agent.
Preferably, the preparation method of the rutile phase hypovanadic oxide ultra-fine nano-powder, in step S4, dry institute
The method used is dry for vacuum drying or air-stream spraying, and drying temperature is 20-250 DEG C.
Preferably, the preparation method of the rutile phase hypovanadic oxide ultra-fine nano-powder, sintering temperature are 300-
800 DEG C, the time of the sintering is 12-15h.
Preferably, the preparation method of the rutile phase hypovanadic oxide ultra-fine nano-powder, keeps the temperature and stirs
10min-72h。
Compared with the prior art, the advantages of the present invention are as follows:
1, preparation method of the invention is relatively cheap without high valuable stuffs, cost of material such as vanadium base alkoxide.
2, preparation method of the invention is not necessarily to reaction under high pressure, and speed of production is fast, and process safety is high.
3, generated waste liquid can be recycled for multiple times in preparation process of the invention, environmental protection and the corresponding dirt of saving
Cost of water treatment.
4, equipment needed for preparation process of the invention is simple, and relative worth is lower, is conducive to the production for controlling corresponding product
Cost.
5, the rutile phase hypovanadic oxide particle that preparation method of the invention obtains is nearly ball-type, and size is small, can control
System is at 20-300 nanometers, good dispersion.
Rutile phase hypovanadic oxide superfine nano particle prepared by the present invention, can be widely used for intelligent temperature control coating, light
Cause the fields such as switch, sensor, reservoir.It is compared with traditional technology, particle purity is high, and size is smaller and uniform, and dispersibility
It well, is the outstanding raw material of high quality Vanadium dioxide intelligent temperature control painting window.
Detailed description of the invention
Fig. 1 is the transmission electron microscope picture for the rutile phase hypovanadic oxide ultra-fine nano-powder that the embodiment of the present invention 1 is prepared；
Fig. 2 is another times magnification for the rutile phase hypovanadic oxide ultra-fine nano-powder that the embodiment of the present invention 1 is prepared
Several transmission electron microscope pictures；
Fig. 3 is the X-ray diffraction for the rutile phase hypovanadic oxide ultra-fine nano-powder that the embodiment of the present invention 1 is prepared
Figure.
Specific embodiment
The present invention will be described in further detail below with reference to the embodiments of the drawings.
A kind of preparation method of rutile phase hypovanadic oxide ultra-fine nano-powder, comprising the following steps:
S1, ammonium hydroxide is added into tetravalence vanadium solution A, stirs to get suspension B；Wherein, the vanadium in the tetravalence vanadium solution A
Ion concentration is 0.1-2mol/L, is dissolved in water by tetravalence vanadic salts, and stir 1-60min with revolving speed 50-2500r/min, preferably
25min is obtained.Wherein tetravalence vanadic salts can be vanadic sulfate, vanadyl oxalate, divanadyl tetrachloride, ascorbic acid vanadyl, citric acid oxygen
Vanadium or tartaric acid vanadyl it is one or more, be also possible to the compound by other vanadium, as vanadic anhydride, ammonium metavanadate or
Tetravalence vanadic salts made of sodium vanadate is restored by reducing agent；Water herein is pure water, distilled water or deionized water；
S2, it is sealed insulated and stirred processing to the suspension B, obtains colloid suspension C, and the holding temperature is not higher than
The boiling point of solvent in tetravalence vanadium solution；
S3, colloid suspension C is separated by solid-liquid separation and is cleaned, obtain hydrated hydroxide vanadyl colloid D；
S4, hydrated hydroxide vanadyl colloid D is dried, and is sintered in protective atmosphere, obtain Rutile Type titanium dioxide
Vanadium ultra-fine nano-powder.
In another embodiment, the preparation method of the rutile phase hypovanadic oxide ultra-fine nano-powder, step S2
Specifically: suspension B is placed in closed container and persistently stirs and be heated to 20-100 DEG C, keeps the temperature and stirs 10min-72h, obtain
To colloid suspension C.
In another embodiment, the preparation method of the rutile phase hypovanadic oxide ultra-fine nano-powder, step S1
In, the additional amount of ammonium hydroxide is, so that ammonium hydroxide content is the 1-30% of suspension quality in the suspension B.
In another embodiment, the preparation method of the rutile phase hypovanadic oxide ultra-fine nano-powder, the step
In rapid S1, before ammonium hydroxide is added into tetravalence vanadium solution A, doped chemical is added into the tetravalence vanadium solution A, is specially
Any one or more in tungsten, molybdenum, magnesium, titanium, iron, niobium, zirconium and fluorine, wherein it is preferred that tungsten, molybdenum, for witch culture, preferably
Raw material is ammonium tungstate, wolframic acid, white tungstic acid and tungsten chloride etc..For molybdenum doping, preferred raw material is ammonium molybdate, molybdic acid etc..
In another embodiment, the preparation method of the rutile phase hypovanadic oxide ultra-fine nano-powder, step S3
In, the separation of solid and liquid uses centrifugal process (centrifuge speed 1000-10000r/min), sedimentation (sedimentation time 1-48
Hour, and solvent help can be added before sedimentation and settle, such as methanol, ethyl alcohol or isopropanol) or membrane filter method (can be used
Metal film, ceramic membrane or organic film are filtered, and the aperture of film is 15-800 nanometers)；In cleaning step, using water, methanol, second
As cleaning agent, the number cleaned repeatedly is 1-10 times for alcohol or isopropanol.
In another embodiment, the preparation method of the rutile phase hypovanadic oxide ultra-fine nano-powder, step S4
In, dry used method is that vacuum drying or air-stream spraying are dry, and for vacuum drying, drying temperature is 20-200 DEG C,
Preferably 40-80 DEG C, the dry duration is 1-48 hours；
Dry for air-stream spraying, drying temperature is 80-250 DEG C, and preferably 120-200 DEG C, spraying revolving speed is 100-
1000r/min。
In another embodiment, the preparation method of the rutile phase hypovanadic oxide ultra-fine nano-powder, sintering temperature
Degree is 300-800 DEG C, preferably 600 DEG C；The time of the sintering is 12-15h, preferably 2 hours.
In another embodiment, the preparation method of the rutile phase hypovanadic oxide ultra-fine nano-powder, heat preservation is simultaneously
Stir 10min-72h.
The principle of the invention lies in when ammonium hydroxide and acid tetravalence vanadic salts reaction, free VO2+ ion and ammonium hydroxide are mentioned
The hydroxyl of confession quickly combines, and generates hydrated hydroxide vanadyl colloid.To generating to obtain hydrated hydroxide under the boiling point lower than solvent
After the processing of vanadyl colloid, colloid will appear certain crystallization, and then obtain that nanoscale rutile phase hypovanadic oxide is ultra-fine to be received
Rice flour body.
Embodiment 1
Prepare the rutile phase hypovanadic oxide ultra-fine nano-powder to undope
1) prepared by colloid suspension:
Vanadic sulfate 4g is taken, 200ml flask is added in powder, 60ml deionized water is added and continues stirring 10 minutes.Add
Enter 10ml concentration and be 25% ammonium hydroxide, and continues stirring and obtain muddy precursor liquid after ten minutes.By the burning equipped with muddy precursor liquid
Bottle sealing, keeps the temperature 2 hours after being heated to 80 DEG C, obtains colloid suspension.
2) colloid is handled:
Colloid suspension obtained in step 1) is transferred in plastic centrifuge tube, centrifuge is put into, in revolving speed 6000r/
It keeps centrifugation to take out after ten minutes under min, removes supernatant, after deionized water is added, sediment is mixed and is put into water
It is ultrasonically treated 5 minutes in supersonic cleaning machine, is put into centrifuge centrifugation, operated repeatedly three times, taken out sediment and be transferred in crucible.
After crucible is put into vacuum oven, vacuum in vacuum oven is kept, drying temperature is set as 60 DEG C, keeps the temperature 24 hours, directly
Sediment is completely dried in crucible.
3) vanadium dioxide is sintered:
Crucible equipped with dry sediment in step 2) is shifted in tube-type atmosphere furnace boiler tube, by being pumped into very in boiler tube
Nitrogen is imported after sky, and after being repeated 3 times, keep nitrogen flow rate 1L per minute.Tube-type atmosphere furnace is begun to warm up from room temperature, is heated up
Rate is 10 DEG C per minute, after temperature rises to 600 DEG C in tube-type atmosphere furnace, 2 hours is kept the temperature, after subsequent cooled to room temperature
It takes out, obtains rutile phase hypovanadic oxide ultra-fine nano-powder.Protective atmosphere in the atmosphere furnace is that high-purity (is not less than
99.8%) inert gas or vacuum, inert gas are nitrogen, carbon dioxide or argon gas, preferably high-purity nitrogen；It can also be with
Some other gases are mixed into according to actual process condition, such as oxygen, carbon monoxide or hydrogen.
Wherein, Fig. 1, Fig. 2 are the obtained rutile phase hypovanadic oxide superfine nanos of the provided preparation method of embodiment 1
The transmission electron microscope picture of powder, it is seen that vanadium dioxide superfine nano particle be it is subsphaeroidal, mean size be 50 nanometers, grain edges are clear
It is clear, have no serious particle agglomeration phenomenon.
Fig. 3 is that the X-ray of the obtained rutile phase hypovanadic oxide ultra-fine nano-powder of the provided preparation method of embodiment 1 spreads out
Penetrate figure, it is seen that obtained ultra-fine nano-powder is the rutile phase hypovanadic oxide of high-purity, and crystallinity is high.
Embodiment 2
Prepare the rutile phase hypovanadic oxide ultra-fine nano-powder of witch culture 1%
1) prepared by colloid suspension:
Vanadic sulfate 4g is taken, 200ml flask is added in powder, 60ml deionized water is added and continues stirring after ten minutes,
0.07g ammonium metatungstate is added.Continue stirring after ten minutes, 10ml concentration is added and is 25% ammonium hydroxide, and continues stirring 10 minutes
After obtain muddy precursor liquid.By the flask sealing equipped with muddy precursor liquid, 2 hours are kept the temperature after being heated to 80 DEG C, obtains colloidal suspension
Turbid.
2) colloid is handled:
Colloid suspension obtained in step 1) is transferred in plastic centrifuge tube, centrifuge is put into, in revolving speed 6000r/
It keeps centrifugation to take out after ten minutes under min, removes supernatant, after deionized water is added, sediment is mixed and is put into water
It is ultrasonically treated 5 minutes in supersonic cleaning machine, is put into centrifuge centrifugation, operated repeatedly three times, taken out sediment and be transferred in crucible.
After crucible is put into vacuum oven, vacuum in vacuum oven is kept, drying temperature is set as 60 DEG C, keeps the temperature 24 hours, directly
Sediment is completely dried in crucible.
3) vanadium dioxide is sintered:
Crucible equipped with dry sediment in step 2) is shifted in tube-type atmosphere furnace boiler tube, by being pumped into very in boiler tube
Nitrogen is imported after sky, and after being repeated 3 times, keep nitrogen flow rate 1L per minute.Tube-type atmosphere furnace is begun to warm up from room temperature, is heated up
Rate is 10 DEG C per minute, after temperature rises to 600 DEG C in tube-type atmosphere furnace, 2 hours is kept the temperature, after subsequent cooled to room temperature
It takes out, obtains rutile phase hypovanadic oxide ultra-fine nano-powder.
Embodiment 3
S1, ammonium hydroxide and acid tetravalence vanadium solution fast reaction, obtain suspension B；
S2, it is sealed insulated and stirred processing to the suspension B, obtains colloid suspension C, and the holding temperature is not higher than
The boiling point of solvent in tetravalence vanadium solution；
S3, colloid suspension C is separated by solid-liquid separation and is cleaned, obtain hydrated hydroxide vanadyl colloid D；
S4, hydrated hydroxide vanadyl colloid D is dried, and is sintered in protective atmosphere, obtain Rutile Type titanium dioxide
Vanadium ultra-fine nano-powder.
Wherein, step S1 specifically: ammonium hydroxide is added into tetravalence vanadium solution A, stirs to get suspension B；Wherein, described four
Vanadium ion concentration in valence vanadium solution A is 0.1-2mol/L, is dissolved in water by tetravalence vanadic salts and obtains.The additional amount of ammonium hydroxide is to make
Obtain the 1-30% that ammonium hydroxide content in the suspension B is suspension quality.
Wherein, step S2 specifically: suspension B is placed in closed container and persistently stirs and be heated to 20-100 DEG C, is protected
Temperature simultaneously stirs, and obtains colloid suspension C.
Wherein, it in the step S1, before ammonium hydroxide is added into tetravalence vanadium solution A, is added into the tetravalence vanadium solution A
A certain amount of cerous nitrate and silica gel solution, wherein cerium molar content is that vanadium molar content is consistent, and silica gel additional amount is so that SiO2
Molar content is 2 times (industrial silicones that silica gel solution herein uses) of vanadium molar content.
In this, cerous nitrate will react with ammonium hydroxide, generate cerium oxide, so that more hollow structures and the strong dioxy of load capacity
SiClx will interact in sintering process, between cerium oxide and vanadium dioxide each other as carrier, so that should
The target product rutile phase hypovanadic oxide ultra-fine nano-powder that method obtains, is not simple hypovanadic oxide powder, tool
Have a purposes: catalysis dimethoxym ethane and methyl acetate obtain methyl acrylate；
Then catalysis reaction is carried out using the target product that the present embodiment 3 obtains, concrete operations are as follows:
It is 1:2, Feed space velocities in the molar ratio of dimethoxym ethane and methyl acetate using the solid phase fixed bed reactor of atmospheric gas-
For 2/h-1, molar ratio 24:1, gas flow 20ml/min, the catalyst amount 0.4g of nitrogen and oxygen, temperature are 350 DEG C
Lower reaction 5.5 hours, reaction result is shown, methyl acrylate selection rate reaches 81%, yield 56%, much higher than conventional test
Selection rate 45%, yield 38%.
In addition to the implementation, all to use equivalent transformation or equivalent replacement the invention also includes there is an other embodiments
The technical solution that mode is formed should all be fallen within the scope of the hereto appended claims.
Claims (10)
1. a kind of preparation method of rutile phase hypovanadic oxide ultra-fine nano-powder, which comprises the following steps:
S1, ammonium hydroxide and acid tetravalence vanadium solution A fast reaction, obtain suspension B；
S2, it is sealed insulated and stirred processing to the suspension B, obtains colloid suspension C, and the holding temperature is not higher than tetravalence
The boiling point of solvent in vanadium solution；
S3, colloid suspension C is separated by solid-liquid separation and is cleaned, obtain hydrated hydroxide vanadyl colloid D；
S4, hydrated hydroxide vanadyl colloid D is dried, and is sintered in protective atmosphere, it is super to obtain rutile phase hypovanadic oxide
Thin nano-powder.
2. the preparation method of rutile phase hypovanadic oxide ultra-fine nano-powder as described in claim 1, which is characterized in that step
S1 specifically: ammonium hydroxide is added into tetravalence vanadium solution A, stirs to get suspension B；Wherein, the vanadium in the tetravalence vanadium solution A from
Sub- concentration is 0.1-2mol/L, is dissolved in water by tetravalence vanadic salts and obtains.
3. the preparation method of rutile phase hypovanadic oxide ultra-fine nano-powder as described in claim 1, which is characterized in that step
S2 specifically: suspension B is placed in closed container and persistently stirs and be heated to 20-100 DEG C, keeps the temperature and stirs, obtain colloid
Suspension C.
4. the preparation method of rutile phase hypovanadic oxide ultra-fine nano-powder as described in claim 1, which is characterized in that described
Tetravalence vanadium solution is vanadic sulfate, vanadyl oxalate, divanadyl tetrachloride, ascorbic acid vanadyl, citric acid vanadyl or tartaric acid vanadyl
It is one or more, or the compound for passing through vanadium includes that vanadic anhydride, ammonium metavanadate or sodium vanadate are restored by reducing agent
Made of tetravalence vanadic salts solution.
5. the preparation method of rutile phase hypovanadic oxide ultra-fine nano-powder as described in claim 1, which is characterized in that step
In S1, the additional amount of ammonium hydroxide is, so that ammonium hydroxide content is the 1-30% of suspension quality in the suspension B.
6. the preparation method of rutile phase hypovanadic oxide ultra-fine nano-powder as described in claim 1, which is characterized in that described
In step S1, before ammonium hydroxide is added into tetravalence vanadium solution A, doped chemical is added into the tetravalence vanadium solution A, is specially
Any one or more in tungsten, molybdenum, magnesium, titanium, iron, niobium, zirconium and fluorine.
7. the preparation method of rutile phase hypovanadic oxide ultra-fine nano-powder as described in claim 1, which is characterized in that
In step S3, described be separated by solid-liquid separation uses centrifugal process, sedimentation or membrane filter method；In cleaning step, using water, methanol,
Ethyl alcohol or isopropanol are as cleaning agent.
8. the preparation method of rutile phase hypovanadic oxide ultra-fine nano-powder as described in claim 1, which is characterized in that step
In S4, dry used method is that vacuum drying or air-stream spraying are dry, and drying temperature is 20-250 DEG C.
9. the preparation method of rutile phase hypovanadic oxide ultra-fine nano-powder as described in claim 1, which is characterized in that sintering
Temperature is 300-800 DEG C, and the time of the sintering is 12-15h.
10. the preparation method of rutile phase hypovanadic oxide ultra-fine nano-powder as claimed in claim 3, which is characterized in that protect
Temperature simultaneously stirs 10min-72h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811407464.9A CN109319838A (en) | 2018-11-23 | 2018-11-23 | A kind of preparation method of rutile phase hypovanadic oxide ultra-fine nano-powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811407464.9A CN109319838A (en) | 2018-11-23 | 2018-11-23 | A kind of preparation method of rutile phase hypovanadic oxide ultra-fine nano-powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109319838A true CN109319838A (en) | 2019-02-12 |
Family
ID=65258706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811407464.9A Pending CN109319838A (en) | 2018-11-23 | 2018-11-23 | A kind of preparation method of rutile phase hypovanadic oxide ultra-fine nano-powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109319838A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110615476A (en) * | 2019-10-24 | 2019-12-27 | 成都先进金属材料产业技术研究院有限公司 | M-phase VO prepared by using failed vanadium battery positive electrolyte2Method (2) |
| CN112209442A (en) * | 2020-10-16 | 2021-01-12 | 成都先进金属材料产业技术研究院有限公司 | Method for preparing M-phase vanadium dioxide nano powder by salt-assisted ultrasonic pyrolysis method |
| CN112209440A (en) * | 2020-10-16 | 2021-01-12 | 成都先进金属材料产业技术研究院有限公司 | Process for preparing M-phase vanadium dioxide nano powder |
| CN112209438A (en) * | 2020-10-16 | 2021-01-12 | 成都先进金属材料产业技术研究院有限公司 | Method for preparing nano vanadium dioxide from ethylene glycol vanadyl |
| CN112239229A (en) * | 2020-10-19 | 2021-01-19 | 成都先进金属材料产业技术研究院有限公司 | Preparation of spherical VO by ultrasonic atomization method2Method and device for preparing nano powder |
| CN112266019A (en) * | 2020-10-16 | 2021-01-26 | 成都先进金属材料产业技术研究院有限公司 | Method for preparing M-phase vanadium dioxide by single ultrasonic atomization homogeneous precipitation method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1837061A (en) * | 2006-03-06 | 2006-09-27 | 复旦大学 | Phase-transition intelligent materials with adjustable phase-transition temperature and process for preparing same |
-
2018
- 2018-11-23 CN CN201811407464.9A patent/CN109319838A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1837061A (en) * | 2006-03-06 | 2006-09-27 | 复旦大学 | Phase-transition intelligent materials with adjustable phase-transition temperature and process for preparing same |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110615476A (en) * | 2019-10-24 | 2019-12-27 | 成都先进金属材料产业技术研究院有限公司 | M-phase VO prepared by using failed vanadium battery positive electrolyte2Method (2) |
| CN112209442A (en) * | 2020-10-16 | 2021-01-12 | 成都先进金属材料产业技术研究院有限公司 | Method for preparing M-phase vanadium dioxide nano powder by salt-assisted ultrasonic pyrolysis method |
| CN112209440A (en) * | 2020-10-16 | 2021-01-12 | 成都先进金属材料产业技术研究院有限公司 | Process for preparing M-phase vanadium dioxide nano powder |
| CN112209438A (en) * | 2020-10-16 | 2021-01-12 | 成都先进金属材料产业技术研究院有限公司 | Method for preparing nano vanadium dioxide from ethylene glycol vanadyl |
| CN112266019A (en) * | 2020-10-16 | 2021-01-26 | 成都先进金属材料产业技术研究院有限公司 | Method for preparing M-phase vanadium dioxide by single ultrasonic atomization homogeneous precipitation method |
| CN112239229A (en) * | 2020-10-19 | 2021-01-19 | 成都先进金属材料产业技术研究院有限公司 | Preparation of spherical VO by ultrasonic atomization method2Method and device for preparing nano powder |
| CN112239229B (en) * | 2020-10-19 | 2022-03-22 | 成都先进金属材料产业技术研究院股份有限公司 | Method and device for preparing spherical VO2 nano powder by ultrasonic atomization method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109319838A (en) | A kind of preparation method of rutile phase hypovanadic oxide ultra-fine nano-powder | |
| Rao et al. | Low-temperature synthesis of TiO2 nanoparticles and preparation of TiO2 thin films by spray deposition | |
| CN105753050B (en) | The preparation method and its particle of rutile phase hypovanadic oxide nano particle | |
| Goutailler et al. | Low temperature and aqueous sol–gel deposit of photocatalytic active nanoparticulate TiO 2 | |
| JP2009521393A (en) | Method for producing metal oxide nanoparticles, and nanoparticles and preparations produced thereby | |
| CN109399711A (en) | A kind of preparation method of rutile phase hypovanadic oxide nano-powder | |
| JP2011178825A (en) | Single crystal fine particle, method for producing the same, and application thereof | |
| JPH10152323A (en) | Crystal titania and its production | |
| JP2004346260A (en) | Thermochromic film and thermochromic glass | |
| JP2011136873A (en) | Vanadium dioxide fine particles, manufacturing method and thermo-chromic film | |
| CN112499984B (en) | Glass coating with near-infrared shielding performance and preparation method thereof | |
| JP4289023B2 (en) | Thermochromic material and thermochromic film or thermochromic glass using the same | |
| Aboualigaledari et al. | A review on the synthesis of the TiO2-based photocatalyst for the environmental purification | |
| CN109336176A (en) | A kind of method that solid phase method largely prepares rutile phase hypovanadic oxide nano-powder | |
| Samadi et al. | Synthesis, characterization, and application of Nd, Zr–TiO 2/SiO 2 nanocomposite thin films as visible light active photocatalyst | |
| CN113877586B (en) | Preparation method and application of cerium-iron bimetallic composite oxide with hierarchical structure and controllable morphology | |
| CN1032585C (en) | Preparation for super fine powder of titanium dioxide | |
| CN105399138A (en) | Perovskite SrTiO3 tetragonal nanoparticle preparation method and product | |
| CN108654663A (en) | A kind of mixed nitrate molten-salt growth method prepares the nitrogen co-doped single-crystal meso-pore TiO of boron2The method of catalysis material | |
| CN101343043A (en) | Amphoteric metal compound nano-material and method of preparing the same | |
| CN101445270A (en) | Preparation of high pure gold redrock nano-titanium dioxide | |
| JP6990153B2 (en) | Manufacturing method of vanadium dioxide | |
| CN106564947B (en) | A kind of continuously grinding grading system for near-infrared reflection titanic oxide material method | |
| CN112342450B (en) | Production process of high-refractive-index coating mixed material | |
| JP7225238B2 (en) | Method for producing vanadium dioxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210115 Address after: 215000 No.288, Ruoshui Road, Suzhou Industrial Park, Suzhou City, Jiangsu Province Applicant after: JITRI INSTITUTE FOR PROCESS MODELLING AND OPTIMIZATION Co.,Ltd. Address before: 215000 No.288, Ruoshui Road, Suzhou Industrial Park, Suzhou City, Jiangsu Province Applicant before: JITRI INSTITUTE FOR PROCESS MODELLING AND OPTIMIZATION Co.,Ltd. Applicant before: FASTEN GROUP Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190212 |
|
| RJ01 | Rejection of invention patent application after publication |