CN105712401A - Calcium vanadate microsphere material and preparation method and application thereof - Google Patents
Calcium vanadate microsphere material and preparation method and application thereof Download PDFInfo
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- CN105712401A CN105712401A CN201610071846.3A CN201610071846A CN105712401A CN 105712401 A CN105712401 A CN 105712401A CN 201610071846 A CN201610071846 A CN 201610071846A CN 105712401 A CN105712401 A CN 105712401A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
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- 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
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- 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
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
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- 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
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/50—Agglomerated particles
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- 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
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- 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
Abstract
The invention discloses a calcium vanadate microsphere material and a preparation method thereof.The chemical constitution of the calcium vanadate microsphere material is Ca2V2O7, calcium vanadate microspheres are assembled by nanoparticles and have a three-dimensional hierarchical structure, and the diameter ranges from 0.5 micrometer to 2 micrometers.The preparation method of the calcium vanadate microsphere material comprises the steps that 1, soluble calcium salt and sodium orthovanadate are prepared into a mixed solution according to the Ca-V mole ratio of 1:(1-3); 2, the pH of the mixed solution is regulated to be 9-10 through an acid solution, uniform stirring is performed, and then reacting is performed for 2-48 h at the temperature of 140 DEG C-200 DEG C to obtain a crude product solution; 3, the crude product solution obtained in the step 2 is cooled to room temperature, and an obtained precipitate is washed and dried to obtain the calcium vanadate microsphere material.According to the preparation method, the pure-phase Ca2V2O7 microsphere material with the three-dimensional hierarchical structure is prepared for the first time.The microsphere material is synthesized through a one-step hydrothermal method and a wet method, the reacting conditions are mild, the technology is simple, controllable in condition and suitable for batched production, and a good technical foundation is laid for application research.
Description
Technical field
The invention belongs to inorganic nano material and preparation method thereof field, be specifically related to a kind of calcium vanadate sphere material with three-dimensional hierarchical structure and its preparation method and application.
Background technology
Calcium vanadate is that a kind of chemical stability is excellent, thermostability and the good inorganic compound of crystal property, there is good optics, electrochemistry and catalysis characteristics, at optics, lithium ion battery, electrochemical sensor and catalytic field, there is good application prospect, cause the widely studied interest of people.Different according to Ca, V, O ratio in material, it is possible to obtain the multiple calcium vanadate material with different composition, structure.Currently, with respect to the research of calcium vanadate material aspect, its composition mainly includes CaV2O6、Ca2V2O7、Ca10V6O25Deng.Wherein, about Ca2V2O7The research report of nano-micrometre material is less, if a small amount of about Ca2V2O7High temperature solid-state method and Hydrothermal Synthesis and photism Quality Research thereof, and adopt the Ca that high temperature solid-state method and water heat transfer go out2V2O7It is erose micron block structure.
In recent years, fast development along with nanotechnology, the three-dimensional hierarchical structure nano/micron material being made up of low dimensional nano-scale cell formation is owing to having the integrated benefit of the single combination generation of nanostructured, Synergy etc., show more excellent physics and chemical characteristic, cause the extensive concern of research worker gradually, become a current important research frontier in the world, but, prior art not yet reports the Ca with three-dimensional hierarchical structure2V2O7Micron ball.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of calcium vanadate sphere material and its preparation method and application, this micron ball is assembled by nano-particle, it adopts one step hydro thermal method, without using any surfactant, technique is simple, easy to operate, has application prospect in light absorbent, electrochemistry etc..
For solving above-mentioned technical problem, the technical solution used in the present invention is:
A kind of calcium vanadate sphere material, its chemical composition is Ca2V2O7, described calcium vanadate micron ball diameter is 0.5 ~ 2 μm, nano-particle assemble, have three-dimensional hierarchical structure.The three-dimensional hierarchical structure micro materials being made up of low dimensional nano-scale cell formation, has integrated benefit, Synergy that the single combination of nanostructured produces, it is contemplated that have physics and the chemical characteristic of excellence.
The diameter of described nano-particle is 50 ~ 100nm.
The preparation method of above-mentioned calcium vanadate sphere material, comprises the following steps:
1. it is that 1:1 ~ 3 are configured to mixed solution by soluble calcium salt and sodium vanadate by Ca:V mol ratio；
2. regulate mixed solution pH for 9 ~ 10 with acid solution, react 2 ~ 48h in 140 ~ 200 DEG C after stirring, obtain the solution of thick product；
3. by step 2. in the solution of the thick product of gained be cooled to room temperature, and by gained washing of precipitate, dry, obtain calcium vanadate sphere material.
Described soluble calcium salt is calcium chloride, calcium nitrate or calcium oxide；The concentration of soluble calcium salt is 0.01 ~ 1mol/L.First soluble calcium salt is prepared into respectively with sodium vanadate solubility solution, then sodium vanadate solution is dropped in solubility calcium saline solution.
Step 2. described in acid be nitric acid, hydrochloric acid or sulphuric acid.The adjustment of pH value is very crucial, and when pH controls when 5.2 ~ 6.2, the chemical composition of its synthetic product is CaV6O16·3H2O, pattern is the membrane material that set of nanowires is dressed up.When pH value is higher than 10, the product of generation no longer has three-dimensional hierarchical structure.
The present invention prepares calcium vanadate micron ball by one step hydro thermal method, and in hydrothermal reaction process, calcium, vanadium, oxygen mix on a molecular scale, obtains the micron ball structure with hierarchy being made up of calcium vanadate nano-particle.
Utilizing ultraviolet-visual spectrometer to have studied its UV-Vis absorption properties, result shows that above-mentioned calcium vanadate sphere material has stronger UV-Vis absorption properties, has application prospect in ultraviolet-visible light district light absorbent.
Adopt having the beneficial effects that of technique scheme generation: (1) present invention is prepared for having three-dimensional hierarchical structure, pure phase Ca first2V2O7Sphere material, enriches Material Field, and provides new material for fields such as optics, electricity, magnetics, quasiconductors；(2) preliminary study micron ball extinction characteristic, result shows that it has stronger UV-Vis absorption properties；(3) present invention adopts one step hydro thermal method, Moist chemical synthesis, and reaction condition is gentle, and technique is simple, condition is controlled, suitable batch produces, and establishes good technique basis for applied research.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the calcium vanadate micron ball prepared according to embodiment 1；
The stereoscan photograph of the calcium vanadate micron ball that Fig. 2 a and Fig. 2 b respectively prepares according to embodiment 1；
Fig. 3 is the calcium vanadate micron ball XRD spectra prepared according to embodiment 2；
Fig. 4 is the stereoscan photograph of the calcium vanadate micron ball prepared according to embodiment 2；
Fig. 5 is the stereoscan photograph of the calcium vanadate micron ball prepared according to embodiment 3；
Fig. 6 is the XRD figure spectrum of the calcium vanadate micron ball prepared according to embodiment 4；
Fig. 7 is the XRD figure spectrum of the calcium vanadate micron ball prepared according to embodiment 5；
Fig. 8 is the stereoscan photograph of the calcium vanadate micron ball prepared according to embodiment 6；
Fig. 9 is the UV-vis DRS figure of the calcium vanadate micron ball prepared according to embodiment 1.
Detailed description of the invention
Embodiment 1
At room temperature, the sodium vanadate of 2mmol is dissolved in 10mL distilled water, by the CaCl of 1mmol2It is dissolved in 8mL distilled water, under magnetic agitation effect, sodium vanadate solution is dropped to CaCl2In solution, stir 10min, with the HNO of 1mol/L3The pH value of reaction system is adjusted to 10 by solution, continue stirring 10min, proceed in the hydrothermal reaction kettle of 25mL afterwards, it is placed in calorstat 180 DEG C of hydro-thermal reaction 12h after sealing, it is cooled to room temperature after completion of the reaction, wash 5 times with the centrifugation respectively of deionized water and dehydrated alcohol, be placed in baking oven by gained precipitation 80 DEG C of dry 8h, obtain Ca2V2O7Sphere material.Above-mentioned product carrying out X-ray diffraction (XRD) analyze, Fig. 1 is XRD spectra, and result shows product diffraction maximum and Ca2V2O7Standard card (JCPDS-ICDDNo.28-0252) matches.Fig. 2 a is scanning electron microscope analysis figure, it was shown that product has micron ball structure, and the diameter of micron ball is about 1 μm, and the scanning electron microscope (SEM) photograph Fig. 2 b amplified further shows that this micron ball is to be assembled by the nano-particle that a large amount of diameters are 50-100nm.
Embodiment 2
At room temperature, the sodium vanadate of 2mmol is dissolved in 7mL distilled water, by the CaCl of 1mmol2It is dissolved in 9mL distilled water, under magnetic agitation effect, sodium vanadate solution is dropped to CaCl2In solution, stir 10min, with the HNO of 1mol/L3Solution continues stirring 10min after the pH value of reaction system is adjusted to 9, proceed in the hydrothermal reaction kettle of 20mL afterwards, it is placed in calorstat 160 DEG C of hydro-thermal reaction 6h after sealing, it is cooled to room temperature after completion of the reaction, after washing 5 times with deionized water and dehydrated alcohol difference centrifugation, it is placed in baking oven in 80 DEG C of dry 12h, obtains Ca2V2O7Sphere material.XRD spectra (Fig. 3) result display product diffraction maximum and Ca2V2O7Match.Being scanned electronic microscope photos (Fig. 4) under bigger enlargement ratio and show that product has micron ball structure, the diameter of micron ball is about 1-1.5 μm, simultaneously it can be observed that this micron ball is to be assembled by the nano-particle that a large amount of diameters are 50-100nm.
Embodiment 3
At room temperature, the sodium vanadate of 1mmol is dissolved in 7mL distilled water, by the CaCl of 1mmol2It is dissolved in 7mL distilled water, under magnetic agitation effect, sodium vanadate solution is dropped to CaCl2In solution, stir 10min, with the HNO of 1mol/L3Solution continues stirring 10min after the pH value of reaction system is adjusted to 10, proceed in the hydrothermal reaction kettle of 20mL afterwards, it is placed in calorstat 160 DEG C of hydro-thermal reaction 48h after sealing, it is cooled to room temperature after completion of the reaction, gained precipitate with deionized water is washed after 6 times to be placed in baking oven by gained precipitation after absolute ethanol washing 5 times 80 DEG C of vacuum drying 8h, obtain Ca2V2O7Sphere material.Scanning electron microscope analysis (Fig. 5) shows that the diameter of micron ball is 0.5-1.0 μm, and each micron ball surface is built-up by less granule.
Embodiment 4
At room temperature, the sodium vanadate of 2mmol is dissolved in 8mL distilled water, by the CaCl of 1mmol2It is dispersed in 8mL distilled water, under magnetic agitation effect, sodium vanadate solution is dropped to CaCl2In dispersion liquid, stir 10min, with the H of 1mol/L2SO4Solution continues stirring 10min after the pH value of reaction system is adjusted to 9, proceed in the hydrothermal reaction kettle of 25mL afterwards, it is placed in calorstat 160 DEG C of hydro-thermal reaction 12h after sealing, it is cooled to room temperature after completion of the reaction, gained precipitate with deionized water and dehydrated alcohol are washed 5 times respectively and is placed in baking oven 60 DEG C of dry 12h, obtain Ca2V2O7Material.XRD spectra (Fig. 6) result display product is Ca2V2O7；Scanning electron microscope analysis shows the micron ball that this product is 1-1.5 μm, and micron ball is to be assembled by the nano-particle that a large amount of diameters are 50-100nm.
Embodiment 5
At room temperature, the sodium vanadate of 4mmol is dissolved in 8mL distilled water, the CaO of 2mmol is dispersed in 8mL distilled water, under magnetic agitation effect, sodium vanadate solution is dropped in CaO dispersion liquid, stir 10min, with the HNO of 1mol/L3Solution continues stirring 10min after the pH value of reaction system is adjusted to 10, proceed in the hydrothermal reaction kettle of 25mL afterwards, it is placed in calorstat 160 DEG C of hydro-thermal reaction 12h after sealing, it is cooled to room temperature after completion of the reaction, after washing 5 times respectively with deionized water and dehydrated alcohol, gained precipitation is placed in baking oven 60 DEG C of vacuum drying 8h, obtains product.XRD spectra (Fig. 7) result display product and Ca2V2O7Standard card matches；Scanning electron microscope analysis shows the micron ball that this product is 1.5-2 μm, and micron ball is to be assembled by the nano-particle that a large amount of diameters are 50-100nm.
Embodiment 6
At room temperature, the sodium vanadate of 1mmol is dissolved in 8mL distilled water, by the CaCl of 0.5mmol2It is dissolved in 5mL distilled water, under magnetic agitation effect, sodium vanadate solution is dropped to CaCl2In solution, stir 10min, with the HNO of 1mol/L3Solution continues stirring 10min after the pH value of reaction system is adjusted to 9, proceed in the hydrothermal reaction kettle of 20mL afterwards, it is placed in calorstat 160 DEG C of hydro-thermal reaction 12h after sealing, it is cooled to room temperature after completion of the reaction, after washing 5 times with deionized water and dehydrated alcohol difference centrifugation, it is placed in baking oven in 80 DEG C of dry 12h, obtains Ca2V2O7Sphere material.XRD test result display product and Ca2V2O7Standard card matches；Being scanned electronic microscope photos (Fig. 8) under bigger enlargement ratio and show that product has micron ball structure, the diameter of micron ball is about 1-1.5 μm, simultaneously it can be observed that this micron ball is to be assembled by the nano-particle that a large amount of diameters are 50-100nm.
Application Example 1
The Ca that will prepare according to embodiment 12V2O7Sphere material carries out UV-Vis DRS (DRS) test, and result is shown in that in Fig. 9, figure, abscissa is wavelength, vertical coordinate statement diffuse-reflectance rate.As can be seen from the figure: calcium vanadate micron ball has an obvious absworption peak within the scope of 450-230nm, it was shown that ultraviolet light is had stronger absorbability by calcium vanadate micron ball.Meanwhile, this material has good stablizing, and can make an addition in the polymeric material such as rubber, plastics and textile material, plays uvioresistant, aging resistance effect, can also be applied to the fields such as photocatalysis, drug release, optics, electricity simultaneously.
Claims (6)
1. a calcium vanadate sphere material, its chemical composition is Ca2V2O7, it is characterised in that described calcium vanadate micron ball diameter is 0.5 ~ 2 μm, nano-particle assemble, have three-dimensional hierarchical structure.
2. calcium vanadate sphere material according to claim 1, it is characterised in that the diameter of described nano-particle is 50 ~ 100nm.
3. the preparation method of the calcium vanadate sphere material described in claim 1, it is characterised in that comprise the following steps:
1. it is that 1:1 ~ 3 are configured to mixed solution by soluble calcium salt and sodium vanadate by Ca:V mol ratio；
2. regulate mixed solution pH for 9 ~ 10 with acid solution, react 2 ~ 48h in 140 ~ 200 DEG C after stirring, obtain the solution of thick product；
3. by step 2. in the solution of the thick product of gained be cooled to room temperature, and by gained washing of precipitate, dry, obtain calcium vanadate sphere material.
4. the preparation method of calcium vanadate sphere material according to claim 3, it is characterised in that step 1. described soluble calcium salt is calcium chloride, calcium nitrate or calcium oxide；The concentration of soluble calcium salt is for for 0.01 ~ 1mol/L.
5. the preparation method of calcium vanadate sphere material according to claim 3, it is characterised in that step 2. described in acid be nitric acid, hydrochloric acid or sulphuric acid.
6. the application in ultraviolet-visible light district light absorbent of the calcium vanadate sphere material described in claim 1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019050472A1 (en) * | 2017-09-08 | 2019-03-14 | National University Of Singapore | A method of producing a nanomaterial from a vanadium source and related nanomaterials |
| CN109553134A (en) * | 2019-01-23 | 2019-04-02 | 陕西科技大学 | A kind of flowers shape calcium vanadate microballoon and preparation method thereof |
| CN111333110A (en) * | 2020-02-24 | 2020-06-26 | 石家庄学院 | Silver-copper-vanadium-oxygen compound nano material and preparation method and application thereof |
-
2016
- 2016-02-02 CN CN201610071846.3A patent/CN105712401B/en not_active Expired - Fee Related
Non-Patent Citations (3)
| Title |
|---|
| JIANFENG GU ET AL.: "Hydrothermal synthesis and luminescent properties of Ca2V2O7:Eu3+ phosphors", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| L. Z. PEI ET AL.: "Controlled Synthesis of Calcium Sulfate and Calcium Vanadate Nanostructures", 《E-J. SURF. SCI. NANOTECH.》 * |
| T. NAKAJIMA ET AL.: "Photoluminescence property of vanadates M2V2O7 (M: Ba, Sr and Ca)", 《OPTICAL MATERIALS》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019050472A1 (en) * | 2017-09-08 | 2019-03-14 | National University Of Singapore | A method of producing a nanomaterial from a vanadium source and related nanomaterials |
| CN109553134A (en) * | 2019-01-23 | 2019-04-02 | 陕西科技大学 | A kind of flowers shape calcium vanadate microballoon and preparation method thereof |
| CN109553134B (en) * | 2019-01-23 | 2021-02-02 | 陕西科技大学 | Flower cluster-shaped calcium vanadate microsphere and preparation method thereof |
| CN111333110A (en) * | 2020-02-24 | 2020-06-26 | 石家庄学院 | Silver-copper-vanadium-oxygen compound nano material and preparation method and application thereof |
| CN111333110B (en) * | 2020-02-24 | 2022-07-19 | 石家庄学院 | Silver-copper-vanadium-oxygen compound nano material and preparation method and application thereof |
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