CN102849797B - Preparation method of V0.6Cr0.4O2 aciculate nanomaterial - Google Patents
Preparation method of V0.6Cr0.4O2 aciculate nanomaterial Download PDFInfo
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- CN102849797B CN102849797B CN201210364767.3A CN201210364767A CN102849797B CN 102849797 B CN102849797 B CN 102849797B CN 201210364767 A CN201210364767 A CN 201210364767A CN 102849797 B CN102849797 B CN 102849797B
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- reaction system
- nanomaterial
- nanometer needle
- aciculate
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Abstract
The invention discloses a preparation method of V0.6Cr0.4O2 aciculate nanomaterial, falling into the technical field of preparation of inorganic material. With vanadium oxide micro-powder and chromium nitrate as materials, under neutral or acid condition, the preparation method directly synthesizes V0.6Cr0.4O2 aciculate nanomaterial by hydrothermal reaction. The preparation method has advantages of nontoxic and harmless materials, no need of reductant and calcining treatment, low cost, simple production process, and easy industrialized large-scale production. The V0.6Cr0.4O2 aciculate nanomaterial has length of micrometer level, diameter of tens of nanometer, high crystallization degree and purity, and consistent product shape under the same preparation conditions. Products of different dimensions can be obtained by regulating reaction system acidity or Cr addition amount within certain range. The nanomaterial can be applied in fields such as catalyst, electrochemical device, sensor, lithium ion battery material, photo-catalytic material, organic synthesis, magnetic recording material, etc.
Description
Technical field
The invention belongs to the preparing technical field of inorganic materials, relate to specifically a kind of V
0.6cr
0.4o
2nanometer needle-like material preparation method.
Background technology
Nano vanadium dioxide material is a kind of important inorganic materials, in fields such as catalyzer, electrochemical appliance, sensor, lithium ion battery material, photocatalyst materials, has broad application prospects.By the doping of other metallic elements, can change its character, widen its range of application, therefore to doping VO
2and preparation method thereof research there is important value.VO
2while adulterating, transformation temperature (Tc) can regulate change, and its variable quantity is relevant with kind and the quantity of doping, and the Cr that for example adulterates increases Tc, V
0.976cr
0.024o
2tc be 72 ℃, often mix the Mo atom that is equivalent to V atomic quantity 1%, Tc reduces 11 ℃, often mixes and is equivalent to V atomic quantity 1%W atom, Tc reduces 26 ℃.Current VO
2the method of doping mainly contains following several:
V
2o
5reduction method is used reduction V in hydrochloric acid medium
2o
5preparation VOCl
2, then further vanadyl basic carbonate ammonium presoma is prepared in reaction, pulverizes, under inert atmosphere, decomposes and obtain VO
2powder, by the Cr that adulterates in presoma, Mo, W, obtains the VO of doping
2, then roasting preparation; Sol-gel method, forms gel by pouring rapid shrend in cold water after vanadium source, dopant material high-temperature fusion into, and then thermal treatment forms xerogel, thermal reduction after grinding, protective atmosphere annealing processing.
Pyrolysis reduction method, ammonium hexavanadate or ammonium meta-vanadate are raw material, add hotchpotch, the vanadium dioxide particles of pyrolysis or doping requires at least 100 ℃ of temperature rise rates/min, difficulty in process, the sample granularity of preparation is micron order.
V
2o
5and WO
3ground and mixed, high temperature reduces under rare gas element, obtains the VO of W modification
2.But these method complex process, and doping is fewer.
For the vanadium oxide nano material of a large amount of chromium modifications, form the V of oxidation chromium-vanadium oxide composite oxides at present
0.6cr
0.4o
2nanometer needle-like material also not studies have reported that.
Summary of the invention
The object of this invention is to provide a kind of V
0.6cr
0.4o
2the preparation method of nanometer needle-like material, prepared V
0.6cr
0.4o
2nanometer needle-like material better crystallinity degree, purity is high, and the shape of product obtaining under same preparation condition is consistent.Can be used for the fields such as catalyzer, electrochemical appliance, sensor, lithium ion battery material, photocatalyst material, find that chromic oxide prepared by this method has ferromegnetism simultaneously, can be applied to magnetic recording material field.
Technical solution of the present invention is as follows:
A kind of V
0.6cr
0.4o
2the preparation method of nanometer needle-like material, as shown in Figure 3, comprises the following steps:
Step 1: the chromium nitrate aqueous solution of preparation 0.01mol/L～0.5mol/L volumetric molar concentration;
Step 2: add VO in the chromium nitrate aqueous solution of preparing in step 1
2micro mist, the molar weight of controlling Cr is 40% ~ 80% of V and Cr molar weight sum, then stirs, and obtains reaction system A;
Step 3: in reaction system A, add appropriate nitric acid, reaction system B, the add-on of nitric acid should make the pH value of reaction system B be acid or neutral;
Step 4: reaction system B is proceeded in teflon-lined water heating kettle, then hydro-thermal reaction 10～72 hours at 140～250 ℃;
Step 5: by solid product filtration, the deionized water wash of step 4 hydro-thermal reaction, then dry at 105～130 ℃, obtain V
0.6cr
0.4o
2nanometer needle-like material.
The present invention utilizes technical grade VO
2micro mist is vanadium source, utilizes chromium nitrate for chromium source, adopts hydro-thermal reaction directly to prepare V under neutrality or acidity
0.6cr
0.4o
2nanometer needle-like material.Raw materials is nontoxic, and preparation process does not need reductive agent, do not need calcination processing, and cost is low, and production technique is simple, is easy to large-scale industrialization and produces.Under hydro-thermal reaction, the disruptive oxidation vanadium particulate of a large amount of chromium ions, forms V ion, and to be then hydrolyzed crystallization be V simultaneously for V ion and Cr ion
0.6cr
0.4o
2nanometer needle-like material.Prepared V
0.6cr
0.4o
2nanometer needle-like length of material is micron dimension, and diameter is ten nanometer scale, better crystallinity degree, and purity is high, and the shape of product obtaining under same preparation condition is consistent.In preparation process, by the pH value of adjusting reaction system, can obtain the V of different scale
0.6cr
0.4o
2nanometer needle-like material; Experiment finds simultaneously, in reaction system A, as long as in the molar weight of Cr is 40% ~ 80% scope of V and Cr molar weight sum mole proportioning of any change Cr and V, products therefrom is all V
0.6cr
0.4o
2, be gained V
0.6cr
0.4o
2the yardstick of nanometer needle-like material is difference (excessive Cr ion has been filtered with ionic forms after hydro-thermal reaction) to some extent.The present invention is the V preparing
0.6cr
0.4o
2nanometer needle-like material can find that chromic oxide prepared by this method has ferromegnetism for fields such as catalyzer, electrochemical appliance, sensor, lithium ion battery material, photocatalyst material, organic syntheses simultaneously, can be applied to magnetic recording material field.
Accompanying drawing explanation
Fig. 1 is V prepared by the present invention
0.6cr
0.4o
2the scanning electron microscope (SEM) photograph of nanometer needle-like material.
Fig. 2 is V prepared by the present invention
0.6cr
0.4o
2the height explanation transmission electron microscope photo of nanometer needle-like material.
Fig. 3 is schematic flow sheet of the present invention.
Embodiment
Embodiment 1
In water heating kettle, add 120ml deionized water, then add 7.23g Cr (NO
3)
39H
2o, stirs until dissolving completely obtains light green clarification chromium nitrate solution.Then add 1.5gVO
2micron particles.Sealing water heating kettle, hydro-thermal reaction is 48 hours at 190 ℃.Product after hydro-thermal reaction is filtered, and deionized water wash, dries, obtains V at 110 ℃
0.6cr
0.4o
2nanometer needle-like material.Ultimate analysis proves that its chemical constitution is V
0.6cr
0.4o
2, nanometer needle-like material product shape is consistent, and better crystallinity degree is about 1.2 μ m, and diameter is about 50nm.
Embodiment 2
The preparation process that adopts above-described embodiment 1, difference is to add 16.87g Cr (NO
3)
39H
2o, obtains V
0.6cr
0.4o
2nanometer needle-like material.Ultimate analysis proves that its chemical constitution is still V
0.6cr
0.4o
2, nanometer needle-like material product shape is consistent, and better crystallinity degree is about 2.0 μ m, and diameter is about 70nm.
Embodiment 3
In water heating kettle, be added in 1000ml deionized water, then add the salpeter solution of the 2mol/L of 20ml, then add 7.23g Cr (NO
3)
39H
2o, stirs until dissolving completely obtains light green clarification chromium nitrate solution.Then add 1.5gVO
2micron particles.Sealing water heating kettle, hydro-thermal reaction is 48 hours at 190 ℃.Product after hydro-thermal reaction is filtered, and deionized water wash, dries at 110 ℃, obtains V
0.6cr
0.4o
2nanometer needle-like material.Ultimate analysis proves that its chemical constitution is V
0.6cr
0.4o
2, nanometer needle-like material product shape is consistent, and better crystallinity degree is about 2.2 μ m, and diameter is about 80nm.
Embodiment 4
In water heating kettle, be added in 1000ml deionized water, then add 100g Cr (NO
3)
39H
2o, stirs until dissolving completely obtains light green clarification chromium nitrate solution.Then add 15gVO
2micron particles.Sealing water heating kettle, hydro-thermal reaction is 24 hours at 160 ℃.Product after hydro-thermal reaction is filtered, and deionized water wash, dries at 110 ℃, obtains V
0.6cr
0.4o
2nanometer needle-like material.Ultimate analysis proves that its chemical constitution is V
0.6cr
0.4o
2, nanometer needle-like material product shape is consistent, and better crystallinity degree is about 1.2 μ m, and diameter is about 50nm.
Claims (3)
1. a V
0.6cr
0.4o
2the preparation method of nanometer needle-like material, comprises the following steps:
Step 1: the chromium nitrate aqueous solution of preparation 0.01mol/L～0.5mol/L volumetric molar concentration;
Step 2: add VO in the chromium nitrate aqueous solution of preparing in step 1
2micro mist, the molar weight of controlling Cr is 40%～80% of V and Cr molar weight sum, then stirs, and obtains reaction system A;
Step 3: add appropriate nitric acid in reaction system A, obtain reaction system B, the add-on of nitric acid should make reaction system B be acid or neutral;
Step 4: reaction system B is proceeded in teflon-lined water heating kettle, then hydro-thermal reaction 10～72 hours at 140～250 ℃;
Step 5: by solid product filtration, the deionized water wash of step 4 hydro-thermal reaction, then dry at 105～130 ℃, obtain V
0.6cr
0.4o
2nanometer needle-like material.
2. V according to claim 1
0.6cr
0.4o
2the preparation method of nanometer needle-like material, is characterized in that, changes the adjustable product V of pH value of reaction system B in acid range
0.6cr
0.4o
2the yardstick of nanometer needle-like material.
3. V according to claim 1
0.6cr
0.4o
2the preparation method of nanometer needle-like material, is characterized in that, in reaction system A, the molar weight of Cr is in 40%～80% scope of V and Cr molar weight sum, to change mole proportioning of Cr and V, adjustable product V
0.6cr
0.4o
2the yardstick of nanometer needle-like material.
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|---|---|---|---|
| CN201210364767.3A CN102849797B (en) | 2012-09-27 | 2012-09-27 | Preparation method of V0.6Cr0.4O2 aciculate nanomaterial |
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|---|---|
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| CN102849797B true CN102849797B (en) | 2014-07-23 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101700909A (en) * | 2009-11-25 | 2010-05-05 | 中国科学技术大学 | Method of preparing intelligent energy-saving vanadium dioxide by hydrothermal method |
| CN102120615A (en) * | 2011-01-21 | 2011-07-13 | 中国科学院上海硅酸盐研究所 | Vanadium dioxide-doped powder and dispersion, and preparation method and application thereof |
| CN102219256A (en) * | 2011-03-03 | 2011-10-19 | 刘爱林 | Thermochromic vanadium dioxide powder and preparation method thereof |
-
2012
- 2012-09-27 CN CN201210364767.3A patent/CN102849797B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101700909A (en) * | 2009-11-25 | 2010-05-05 | 中国科学技术大学 | Method of preparing intelligent energy-saving vanadium dioxide by hydrothermal method |
| CN102120615A (en) * | 2011-01-21 | 2011-07-13 | 中国科学院上海硅酸盐研究所 | Vanadium dioxide-doped powder and dispersion, and preparation method and application thereof |
| CN102219256A (en) * | 2011-03-03 | 2011-10-19 | 刘爱林 | Thermochromic vanadium dioxide powder and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| A New Metastable Phase of Crystallized V2O4·0.25H2O Nanowires: Synthesis and Electrochemical Measurements;Mingdeng Wei et al.;《Adv. Mater.》;20051103;第17卷;2964–2969 * |
| Depressed Phase Transition in Solution-Grown VO2 Nanostructures;Luisa Whittaker et al.;《 J. Am. Chem. Soc.》;20090608;第131卷(第25期);8884–8894 * |
| Luisa Whittaker et al..Depressed Phase Transition in Solution-Grown VO2 Nanostructures.《 J. Am. Chem. Soc.》.2009,第131卷(第25期),8884–8894. |
| Mingdeng Wei et al..A New Metastable Phase of Crystallized V2O4·0.25H2O Nanowires: Synthesis and Electrochemical Measurements.《Adv. Mater.》.2005,第17卷2964–2969. |
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Owner name: SICHUAN INSTITUTE OF PIEZOELECTRIC AND ACOUSTOOPTI Effective date: 20130307 |
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Inventor after: Li Zhijie Inventor after: Zu Xiaotao Inventor after: Ma Jinyi Inventor after: Yang Jing Inventor before: Li Zhijie Inventor before: Zu Xiaotao |
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Effective date of registration: 20130307 Address after: 611731 Chengdu province high tech Zone (West) West source Avenue, No. 2006 Applicant after: University of Electronic Science and Technology of China Applicant after: SICHUAN?INSTITUTE?OF?PIEZOELECTRIC?AND?ACOUSTOOPTIC?TECHNOLOGY Address before: 611731 Chengdu province high tech Zone (West) West source Avenue, No. 2006 Applicant before: University of Electronic Science and Technology of China |
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