CN106966432B - There is the Mx ' phases VO of metallic character under normal pressure2The preparation method of nano material - Google Patents
There is the Mx ' phases VO of metallic character under normal pressure2The preparation method of nano material Download PDFInfo
- Publication number
- CN106966432B CN106966432B CN201710345566.1A CN201710345566A CN106966432B CN 106966432 B CN106966432 B CN 106966432B CN 201710345566 A CN201710345566 A CN 201710345566A CN 106966432 B CN106966432 B CN 106966432B
- Authority
- CN
- China
- Prior art keywords
- phases
- preparation
- metallic character
- nano material
- nano particle
- 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.)
- Expired - Fee Related
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
-
- 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
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- 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
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
There is the Mx' phases VO of metallic character under the normal pressure of the present invention2The preparation method of nano material, belong to the technical field of nano material preparation.For the present invention with vanadic anhydride, oxalic acid and sodium tungstate are starting material, and the vanadium dioxide nano particle of witch culture is prepared through hydro-thermal and calcining；Through excess pressure up to~64GPa processing after release, obtain it is being stabilized at normal temperatures and pressures, have metallic character Mx' phases VO2Nano material.The inventive method is simple, easily operated；The sample topography of preparation is homogeneous, good crystallinity, the VO with other structures2Compare, mix the VO of tungsten2(Mx') mutually the structure of sample keeps constant after metal is changed into, thus has more preferable stability during insulator-metal transition, has certain application prospect.
Description
Technical field
The invention belongs to prepare VO2The technical field of nano material, and in particular to utilize the VO of witch culture2(R) nanometer
Grain prepares the VO with metallic character by the method for high pressure2The new method of nano material.
Background technology
VO2It is a kind of important functional material, there is the properties such as unique electricity, optics and magnetics, in intelligent glass, electricity
Learning the fields such as switch, gas sensing resistance, lithium battery data storage has important application prospect.In nature, there is semiconductor
The VO of characteristic2Crystal has many kinds, including：VO2(M1)、VO2(A)、 VO2(B)、VO2And VO (C)2(D), however, having metal
The VO of characteristic2Crystal only has VO2(R).Recently as the continuous development of material preparation technology, more new VO have been prepared2
Structure, such as by adulterating obtained M2, M3 and T-phase, but these structures are semiconductor phase.So far, there is metal
Characteristic VO2The preparation of material is still a challenging job.
High pressure can effectively adjust material structure and property, be prepare the material with new construction, new property one kind it is new
Method.At present, people have begun to explore various VO that may be present using the means of high pressure2New construction.Under high pressure, it is real
Test and have discovered that M1', Mx phase VO with metallic character2Paramorph, still, these metal phases are in stress-relief process
The middle M1 phases being changed into respectively with characteristic of semiconductor and another can be stabilized at ambient pressure, with characteristic of semiconductor
New construction Mx' phases.Up to the present, domestic and foreign countries are there is not yet relevant to VO2(Mx') the research report in terms of W doping is carried out
Road.
The content of the invention
The purpose of the present invention is provided with one kind using doping and high pressure tactics to prepare with metallic character Mx' phases VO2Receive
The method of rice material.With the R phases VO of witch culture2Nano particle is raw material, and being obtained by HIGH PRESSURE TREATMENT under normal pressure has metal special
The Mx' phases VO of property2The method of nano particle.
Its step can be：Using the diamond anvil cell press precompressed rhenium piece that anvil face is 200 μm, and in impression centre drill
A diameter of 100 μm of hole.The R phases VO that appropriate W is adulterated2Nano particle is filled into the hole of rhenium piece, then adds ruby
Microballoon is as pressure mark (pressure of detection pressure intracavitary), and first/alcohol mixed solution that dropwise addition volume ratio is 4: 1 is as transmission medium
Or hard pressure, press is sealed, is pressurizeed.When pressure rise is to~64GPa, unloads and be depressed into normal pressure, you can obtain with metal
The Mx' phases VO of characteristic2Nano particle.Specific preparation process is summarized as follows.
There is the Mx' phases VO of metallic character under a kind of normal pressure2The preparation method of nano material, with diamond anvil cell press
For pressue device；The R phases VO adulterated with W2Nano particle is raw material；Raw material is filled up into sample cavity, or raw material is filled into sample
First/alcohol mixed solution is added dropwise as transmission medium in chamber again, is pressurizeed；The release when pressure rise is to 64GPa or higher, is obtained
To the Mx' phases VO with metallic character2Nano particle.
Described first/alcohol mixed solution can be methanol, the mixed solution that ethanol volume ratio is 4: 1.
The R phases VO of witch culture used in the present invention2Nanoparticle raw materials are preferably prepared by following processes：By V2O5, grass
Acid and Na2WO4·2H2O is added in deionized water, is stirred to transparent, and wherein W and V mol ratio are 10:100；It is then transferred into
Sealed in reactor, 24 hours are incubated at 190 DEG C；Reaction terminates rear natural cooling, and product is washed with alcohol and deionized water,
After vacuum drying argon gas protection under 600 DEG C calcine 3 hours.
In the present invention, the VO for the witch culture that prior art is prepared2(R) although nano particle can be used for preparing with gold
Belong to the Mx' phases VO of characteristic2Nano particle, but the effect method more of the invention that provides is far short of what is expected.Therefore to the VO of witch culture2(R) nanometer
The reactant species and course of reaction of the preparation process of particle have carried out further adjustment.Five oxygen are thought in preparation process of the present invention
Change that two vanadium are vanadium source, oxalic acid is reducing agent, sodium tungstate is tungsten source, course of reaction is hydro-thermal and calcination method.Reacted in hydro-thermal reaction
The filling rate of thing solution in a kettle is 0.6, reaction temperature is 190 DEG C, the reaction time is 24 hours.Hydrothermal product is through washing
Wash, be freeze-dried after in argon atmosphere 600 DEG C calcining 3h, you can obtain the VO of homogeneous, good crystallinity the witch culture of pattern2
(R) nano particle.
The present invention prepared first witch culture, have metallic character Mx' phases VO2Nano particle；Experimental method letter
It is single, it is easily operated；The sample topography of preparation is homogeneous, good crystallinity.With the VO of other structures2Compare, mix the VO of tungsten2(Mx') mutually exist
The structure for being changed into sample after metal keeps constant, thus has more preferable stability during insulator-metal transition, because
This has broad application prospects.
Brief description of the drawings
Fig. 1 is the VO of witch culture made from embodiment 12(R) electromicroscopic photograph of nanoparticle raw materials.
Fig. 2 is the VO of witch culture made from embodiment 12(R) the x-ray diffraction spectrogram of nanoparticle raw materials.
Fig. 3 is the obtained Mx' phases VO with metallic character of embodiment 22The electromicroscopic photograph of nano particle.
Fig. 4 is the obtained Mx' phases VO with metallic character of embodiment 22The X-ray diffraction spectrogram of nano particle.
Fig. 5 is the obtained Mx' phases VO with metallic character of embodiment 22The infrared spectrogram of nano particle.
Fig. 6 is the obtained Mx' phases VO with metallic character of embodiment 32The infrared spectrogram of nano particle.
Fig. 7 is the obtained VO with characteristic of semiconductor of embodiment 42(Mx') X-ray diffraction spectrogram.
Fig. 8 is the obtained VO with characteristic of semiconductor of embodiment 52(Mx') infrared spectrogram.
Embodiment
The present invention is expanded on further with reference to specific embodiment.
Embodiment 1
VO2(R) preparation process of nano particle is as follows：By 0.2275g V2O5, 0.3938g oxalic acid, 0.0825g
Na2WO4·2H2It is 10 that O, which is added and filled the mol ratio in beaker, making W and V in reactant in 100ml deionized waters,:100, utilize
Magnetic stirring apparatus stirs obtained reactant solution to transparent, is then transferred into 50ml reactor, filling rate 0.6,
And it is incubated 24 hours at 190 DEG C.Question response naturally cools to room temperature after terminating, take out product, utilize alcohol and deionized water
Low-temperature vacuum drying 24 hours in freeze drier are placed in after washing for several times.Finally, the product after taking-up drying process exists
Calcined 3 hours at 600 DEG C under the protection of argon gas.The VO of witch culture made from the present embodiment2(R) Electronic Speculum of nanoparticle raw materials
Photo is shown in Fig. 1, and x x ray diffraction spectrograms are shown in Fig. 2.The VO of obtained witch culture2(R) nano particle has cubic rutile structure.
Embodiment 2：
Using the diamond anvil cell press precompressed rhenium piece that anvil face is 200 μm, and a diameter of 100 μm in impression centre drill
Hole, sample cavity of the hole as charging feedstock.By the R phases VO of witch culture made from appropriate embodiment 12Nano particle
Raw material is filled into sample cavity, then adds ruby microballoon as pressure mark (pressure of detection pressure intracavitary), and it is 4: 1 that volume ratio, which is added dropwise,
First/alcohol mixed solution as transmission medium, then seal press, pressurizeed.When pressure rise to~64GPa, release
To normal pressure, the VO of Mx' phases with metallic character can be obtained2Nano particle.The obtained Mx' phases VO with metallic character2Nanometer
Particle electromicroscopic photograph, X-ray diffraction spectrum and infrared spectrum are shown in Fig. 3, Fig. 4 and Fig. 5.
Embodiment 3：
Press, sample cavity and transmission medium are the same as embodiment 2.By the R phases VO of witch culture made from embodiment 12Nano particle
Raw material fills up sample cavity, then adds ruby microballoon as pressure mark (pressure of detection pressure intracavitary), then seals press, is added
Pressure.When pressure rise to~65.5GPa, unload and be depressed into normal pressure, the VO of Mx' phases with metallic character can be obtained2Nano particle, system
The Mx' phases VO with metallic character obtained2The infrared spectrum of nano particle is shown in Fig. 6.
Embodiment 4：
Press, sample cavity and transmission medium are the same as embodiment 2.By in right amount undoped with VO2(M1) body material feedstock is filled into
In sample cavity, then ruby microballoon is added as pressure mark (pressure of detection pressure intracavitary), first/ethanol that volume ratio is 4: 1 is added dropwise
Then mixed solution is sealed press, pressurizeed as transmission medium.When pressure rise to~64GPa, unload and be depressed into normal pressure, obtain
To the VO with characteristic of semiconductor2(Mx').The obtained VO with characteristic of semiconductor2(Mx') X-ray diffraction spectrum is shown in Fig. 7.This
Embodiment shows VO as counter-example2(M1) body material feedstock can not prepare the VO with metallic character2(Mx').
Embodiment 5：
Press, sample cavity and transmission medium are the same as embodiment 2.By in right amount undoped with VO2(M1) body material feedstock fills up sample
Product chamber, then ruby microballoon is added as pressure mark (pressure of detection pressure intracavitary), press is then sealed, is pressurizeed.Work as pressure
~69GPa is increased to, unloads and is depressed into normal pressure, obtains the VO with characteristic of semiconductor2(Mx').It is obtained with characteristic of semiconductor
VO2(Mx') infrared spectrum is shown in Fig. 8.The present embodiment shows VO as counter-example2(M1) body material feedstock can not be prepared with metal
The VO of characteristic2(Mx').
Claims (3)
1. there is the Mx' phases VO of metallic character under a kind of normal pressure2The preparation method of nano material, using diamond anvil cell press as
Pressue device；Characterized in that, the R phases VO adulterated with W2Nano particle is raw material；Raw material is filled up into sample cavity, or raw material is filled out
It is attached to sample cavity and first/alcohol mixed solution is added dropwise again as transmission medium, is pressurizeed；In pressure rise to 64~65.5GPa
When release, obtain the Mx' phases VO with metallic character2Nano particle.
2. there is the Mx' phases VO of metallic character under normal pressure according to claim 12The preparation method of nano material, its feature
It is, described first/alcohol mixed solution, is methanol, the mixed solution that ethanol volume ratio is 4: 1.
3. there is the Mx' phases VO of metallic character under normal pressure according to claim 1 or 22The preparation method of nano material, its
It is characterised by, the R phases VO of witch culture2Prepared by the process of nanoparticle raw materials, be by V2O5, oxalic acid and Na2WO4·2H2O is added and gone
In ionized water, stir to transparent, wherein W and V mol ratio are 10:100；It is then transferred into reactor and seals, at 190 DEG C
Insulation 24 hours；Reaction terminates rear natural cooling, and product is washed with alcohol and deionized water, after freeze-drying under argon gas protection
600 DEG C are calcined 3 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710345566.1A CN106966432B (en) | 2017-05-17 | 2017-05-17 | There is the Mx ' phases VO of metallic character under normal pressure2The preparation method of nano material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710345566.1A CN106966432B (en) | 2017-05-17 | 2017-05-17 | There is the Mx ' phases VO of metallic character under normal pressure2The preparation method of nano material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106966432A CN106966432A (en) | 2017-07-21 |
| CN106966432B true CN106966432B (en) | 2018-03-09 |
Family
ID=59325779
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710345566.1A Expired - Fee Related CN106966432B (en) | 2017-05-17 | 2017-05-17 | There is the Mx ' phases VO of metallic character under normal pressure2The preparation method of nano material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106966432B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7225238B2 (en) * | 2018-07-31 | 2023-02-20 | 日本化学工業株式会社 | Method for producing vanadium dioxide |
| CN109205575B (en) * | 2018-09-27 | 2021-06-08 | 吉林大学 | Amorphous Cr under normal pressure2Ge2Te6Method for producing a material |
| CN109437302A (en) * | 2018-11-09 | 2019-03-08 | 吉林大学 | It is a kind of to prepare the spherical porous pattern V of different-diameter size2O5Method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295312A (en) * | 2010-06-22 | 2011-12-28 | 中国科学院合肥物质科学研究院 | Tungsten-doped vanadium dioxide nanopowder and preparation method for the same |
| CN102912308A (en) * | 2012-10-25 | 2013-02-06 | 深圳大学 | Process for manufacturing vanadium dioxide thin film with low phase-transition temperature |
| CN103043722A (en) * | 2013-01-30 | 2013-04-17 | 武汉大学 | Method for transforming vanadium dioxide from B phase to doped M phase |
| CN105624630A (en) * | 2016-03-26 | 2016-06-01 | 上海大学 | Preparation method of VO2 by using VOx/M/VOx sandwich structure film and application of VO2 |
| CN106083044A (en) * | 2016-06-17 | 2016-11-09 | 华中科技大学 | Monoclinic phase VO2the fast preparation method of metal insulator Phase transformation ceramics material |
-
2017
- 2017-05-17 CN CN201710345566.1A patent/CN106966432B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295312A (en) * | 2010-06-22 | 2011-12-28 | 中国科学院合肥物质科学研究院 | Tungsten-doped vanadium dioxide nanopowder and preparation method for the same |
| CN102912308A (en) * | 2012-10-25 | 2013-02-06 | 深圳大学 | Process for manufacturing vanadium dioxide thin film with low phase-transition temperature |
| CN103043722A (en) * | 2013-01-30 | 2013-04-17 | 武汉大学 | Method for transforming vanadium dioxide from B phase to doped M phase |
| CN105624630A (en) * | 2016-03-26 | 2016-06-01 | 上海大学 | Preparation method of VO2 by using VOx/M/VOx sandwich structure film and application of VO2 |
| CN106083044A (en) * | 2016-06-17 | 2016-11-09 | 华中科技大学 | Monoclinic phase VO2the fast preparation method of metal insulator Phase transformation ceramics material |
Non-Patent Citations (1)
| Title |
|---|
| The pressure-induced metallization of monoclinic vanadium dioxide;Huafang Zhang，et al.;《RSC Adv.》;20161231;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106966432A (en) | 2017-07-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Preparation and characterization of ZrO2: Eu3+ phosphors | |
| CN106966432B (en) | There is the Mx ' phases VO of metallic character under normal pressure2The preparation method of nano material | |
| Li et al. | Preparation and characteristics of nanocrystalline NiO by organic solvent method | |
| Feng et al. | Ordered mesoporous WO 3 film with outstanding gasochromic properties | |
| Li et al. | A novel method for preparation of doped Ba3 (Ca1. 18Nb1. 82) O9− δ: Application to ammonia synthesis at atmospheric pressure | |
| CN103050640B (en) | A kind of preparation method of nanorod with zinc oxide nano-particle/silicodioxide dioxide composite structure | |
| Teng et al. | One-pot hydrothermal synthesis of uniformly cubic Co3O4 nanocrystals | |
| Devaraju et al. | Eu3+: Y2O3 microspheres and microcubes: A supercritical synthesis and characterization | |
| Liu et al. | Soft-chemistry synthesis of LiNbO3 crystallites | |
| CN101857272A (en) | Preparation method for micro-nano acicular structural KNbO3 | |
| Xiong et al. | Synthesis and luminescence properties of hand-like α-Bi2O3 microcrystals | |
| Zhang et al. | A facile synthesis of Co3O4 nanoflakes: magnetic and catalytic properties | |
| Venkatachalam et al. | Synthesis of Er3+ doped Y2O3 nanophosphors | |
| CN105329948A (en) | Novel preparation method for gamma-MnOOH of net structure | |
| Gallini et al. | Synthesis and characterization of monazite-type Sr: LaPO4 prepared through coprecipitation | |
| CN101941734A (en) | Tin oxide nanomaterial and preparation method thereof | |
| Foo et al. | Synthesis and characterisation of Y2O3 using ammonia oxalate as a precipitant in distillate pack co-precipitation process | |
| Cheng et al. | A facile method to fabricate porous Co3O4 hierarchical microspheres | |
| He et al. | Preparation of porous cobalt aluminate and its chromogenic mechanism | |
| Ghoshal et al. | Synthesis of ZnO nanoparticles by solvothermal method and their ammonia sensing properties | |
| CN106753365A (en) | It is a kind of that BiPO is synthesized by Surfactant CTAB auxiliary4:Eu3+Fluorescent material and its method | |
| Liu et al. | A new solvothermal method of preparing V O2 nanosheets and petaloid clusters | |
| Xin et al. | Synthesis and characteristics of nanocrystalline YSZ by homogeneous precipitation and its electrical properties | |
| CN105152226A (en) | Preparation and application of magnetic nanoring microwave absorbing agent | |
| Zhang et al. | Low-temperature synthesis of superfine barium strontium titanate powder by the citrate method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180309 Termination date: 20200517 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |