CN105712401B - Calcium vanadate sphere material and its preparation method and application - Google Patents

Calcium vanadate sphere material and its preparation method and application Download PDF

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CN105712401B
CN105712401B CN201610071846.3A CN201610071846A CN105712401B CN 105712401 B CN105712401 B CN 105712401B CN 201610071846 A CN201610071846 A CN 201610071846A CN 105712401 B CN105712401 B CN 105712401B
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calcium
vanadate
solution
preparation
sphere material
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CN105712401A (en
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张绍岩
侯梦华
候玲玲
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Shijiazhuang University
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00Compounds of vanadium
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/70Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72Crystal-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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/80Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/84Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/30Particle morphology extending in three dimensions
    • C01P2004/32Spheres
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/50Agglomerated particles
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/61Micrometer sized, i.e. from 1-100 micrometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/62Submicrometer sized, i.e. from 0.1-1 micrometer

Abstract

The invention discloses a kind of calcium vanadate sphere material and preparation method thereof, its chemical composition is Ca2V2O7, the calcium vanadate micron ball assembles by nano particle, has a three-dimensional hierarchical structure, a diameter of 0.5 ~ 2 μm.Its preparation method includes:1. soluble calcium salt and sodium vanadate are pressed into Ca:V mol ratios are 1:1 ~ 3 is configured to mixed solution;2. adjusting mixed solution pH as 9 ~ 10 using acid solution, stir and react 2 ~ 48h after 140 ~ 200 DEG C, obtain the solution of crude product;3. the solution of step 2. middle gained crude product is cooled into room temperature, by gained washing of precipitate, drying, calcium vanadate sphere material is obtained.The present invention is prepared for having three-dimensional hierarchical structure, pure phase Ca first2V2O7Sphere material, for the present invention using one step hydro thermal method, Moist chemical synthesis, reaction condition is gentle, and technique is simple, condition is controllable, suitable batch production, and good technique basis is established for application study.

Description

Calcium vanadate sphere material and its preparation method and application
Technical field
The invention belongs to inorganic nano material and preparation method thereof field, and in particular to a kind of with three-dimensional hierarchical structure Calcium vanadate sphere material and its preparation method and application.
Background technology
Calcium vanadate is a kind of excellent chemical stability, heat resistance and the good inorganic compound of crystal property, is had good Optics, electrochemistry and catalysis characteristics, have in optics, lithium ion battery, electrochemical sensor and catalytic field fine Application prospect, cause the widely studied interest of people.It is different according to Ca, V, O ratio in material, it can obtain a variety of having Different composition, the vanadic acid calcium material of structure.At present, the research in terms of vanadic acid calcium material, its composition mainly include CaV2O6、Ca2V2O7、Ca10V6O25Deng.Wherein, on Ca2V2O7The research report of nano-micrometre material is less, as long as a small amount of close In Ca2V2O7High temperature solid-state method and Hydrothermal Synthesiss and its photism Quality Research, and closed using high temperature solid-state method and hydro-thermal method Into the Ca gone out2V2O7It is the micron block structure of irregular shape.
In recent years, with the fast development of nanometer technology, the three-dimensional classification being made up of low dimensional nano-scale cell formation Structure nano/micron material is due to integrated benefit, Synergy etc. caused by the single combination of nanostructured, showing more excellent Different physics and chemical characteristic, gradually cause the extensive concern of researcher, become at present in the world one it is important Research frontier, however, prior art not yet reports the Ca with three-dimensional hierarchical structure2V2O7Micron ball.
The content of the invention
, should 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 Micron ball is assembled by nano particle, and it uses one step hydro thermal method, without using any surfactant, and technique is simple, behaviour Facilitate, there is application prospect in light absorbent, electrochemistry etc..
In order to solve the above technical problems, the technical solution adopted by the present invention is:
A kind of calcium vanadate sphere material, its chemical composition are Ca2V2O7, a diameter of 0.5 ~ 2 μ of calcium vanadate micron ball M, assembled by nano particle, there is three-dimensional hierarchical structure.The three-dimensional classification being made up of low dimensional nano-scale cell formation Structure micro materials, there is integrated benefit, Synergy caused by the single combination of nanostructured, it is contemplated that have excellent physics and Chemical characteristic.
A diameter of 50 ~ 100nm of the nano particle.
The preparation method of above-mentioned calcium vanadate sphere material, comprises the following steps:
1. soluble calcium salt and sodium vanadate are pressed into Ca:V mol ratios are 1:1 ~ 3 is configured to mixed solution;
2. adjusting mixed solution pH as 9 ~ 10 using acid solution, stir and react 2 ~ 48h after 140 ~ 200 DEG C, obtain and slightly produce The solution of product;
3. the solution of step 2. middle gained crude product is cooled into room temperature, and by gained washing of precipitate, drying, obtain calcium vanadate Sphere material.
The soluble calcium salt is calcium chloride, calcium nitrate or calcium oxide;The concentration of soluble calcium salt is 0.01 ~ 1mol/L. Soluble calcium salt and sodium vanadate are prepared into soluble solution respectively first, sodium vanadate solution is then added dropwise to solubility In calcium salt soln.
Step 2. described in acid be nitric acid, hydrochloric acid or sulfuric acid.The regulation of pH value is very crucial, when pH is controlled 5.2 ~ 6.2, The chemical composition of its synthetic product is CaV6O16·3H2O, pattern are the membrane material that nano wire is assembled into.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 calcium, vanadium, oxygen are in molecular water in hydrothermal reaction process Flat upper mixing, obtains the micron spherical structure with hierarchy being made up of vanadic acid calcium nano.
Its UV-Vis absorption properties is have studied using ultraviolet-visual spectrometer, the results showed that above-mentioned calcium vanadate micron Ball material has stronger UV-Vis absorption properties, has application prospect in ultraviolet-visible light area light absorbent.
It is using beneficial effect caused by above-mentioned technical proposal:(1)The present invention is prepared for that there is three-dimensional classification to tie first Structure, pure phase Ca2V2O7Sphere material, Material Field is enriched, and provided for fields such as optics, electricity, magnetics, semiconductors New material;(2)Primary Study micron ball extinction characteristic, the results showed that it has stronger UV-Visible absorption Energy;(3)The present invention is using one step hydro thermal method, Moist chemical synthesis, and reaction condition is gentle, and technique is simple, condition is controllable, the life of suitable batch Production, good technique basis is established for application study.
Brief description of the drawings
Fig. 1 is the XRD spectra according to calcium vanadate micron ball made from embodiment 1;
Fig. 2 a and Fig. 2 b are respectively the stereoscan photograph according to calcium vanadate micron ball made from embodiment 1;
Fig. 3 is according to calcium vanadate micron ball XRD spectra made from embodiment 2;
Fig. 4 is the stereoscan photograph according to calcium vanadate micron ball made from embodiment 2;
Fig. 5 is the stereoscan photograph according to calcium vanadate micron ball made from embodiment 3;
Fig. 6 is the XRD spectrum according to calcium vanadate micron ball made from embodiment 4;
Fig. 7 is the XRD spectrum according to calcium vanadate micron ball made from embodiment 5;
Fig. 8 is the stereoscan photograph according to calcium vanadate micron ball made from embodiment 6;
Fig. 9 is the UV-vis DRS figure according to calcium vanadate micron ball made from embodiment 1.
Embodiment
Embodiment 1
At room temperature, 2mmol sodium vanadate is dissolved in 10 mL distilled water, by 1mmol CaCl2It is dissolved to 8 In mL distilled water, under magnetic agitation effect, sodium vanadate solution is added dropwise to CaCl2In solution, 10 min are stirred, with 1mol/L HNO3The pH value of reaction system is adjusted to 10 by solution, is continued to stir 10 min, is transferred to 25 mL hydro-thermal reaction afterwards 180 DEG C of hydro-thermal reaction 12h in insulating box are placed in kettle, after sealing, room temperature is cooled to after completion of the reaction, uses deionized water And absolute ethyl alcohol centrifuges washing 5 times respectively, gained precipitation is placed in 80 DEG C of dry 8h in baking oven, obtains Ca2V2O7Micron Ball material.Above-mentioned product is subjected to X-ray diffraction(XRD)Analysis, Fig. 1 is XRD spectra, as a result show product diffraction maximum and Ca2V2O7Standard card(JCPDS-ICDD No. 28-0252)Match.Fig. 2 a are scanning electron microscope analysis figure, show that product has There is a micron spherical structure, a diameter of 1 μm or so of micron ball, the scanning electron microscope (SEM) photograph Fig. 2 b further amplified show that the micron ball is Assembled by a large amount of a diameter of 50-100nm nano particle.
Embodiment 2
At room temperature, 2mmol sodium vanadate is dissolved in 7 mL distilled water, by 1mmol CaCl2It is dissolved to 9mL In distilled water, under magnetic agitation effect, sodium vanadate solution is added dropwise to CaCl2In solution, 10 min are stirred, with 1mol/L HNO3Solution continues to stir 10 min after the pH value of reaction system is adjusted into 9, is transferred to afterwards in 20 mL hydrothermal reaction kettle, 160 DEG C of hydro-thermal reaction 6h in insulating box are placed on after sealing, are cooled to room temperature after completion of the reaction, with deionized water and anhydrous Ethanol centrifuge respectively washing 5 times after, be placed in baking oven in 80 DEG C of dry 12h, obtain Ca2V2O7Sphere material.XRD is composed Figure(Fig. 3)As a result product diffraction maximum and Ca are shown2V2O7Match.Electronic microscope photos is scanned under larger enlargement ratio(Fig. 4) Show that product has micron spherical structure, the diameter of micron ball is about 1-1.5 μm, is observed that simultaneously:The micron ball is by big Measure what a diameter of 50-100nm nano particle assembled.
Embodiment 3
At room temperature, 1mmol sodium vanadate is dissolved in 7 mL distilled water, by 1mmol CaCl2It is dissolved to 7 In mL distilled water, under magnetic agitation effect, sodium vanadate solution is added dropwise to CaCl2In solution, 10 min are stirred, with 1mol/L HNO3Solution continues to stir 10 min after the pH value of reaction system is adjusted into 10, and the hydro-thermal for being transferred to 20 mL afterwards is anti- Answer in kettle, 160 DEG C of h of hydro-thermal reaction 48 in insulating box are placed on after sealing, room temperature is cooled to after completion of the reaction, gained is sunk Shallow lake is washed with deionized after 6 times washed 5 times with absolute ethyl alcohol after gained precipitation is placed in baking oven 80 DEG C of vacuum drying 8h, Obtain Ca2V2O7Sphere material.Scanning electron microscope analysis(Fig. 5)Show a diameter of 0.5-1.0 μm of micron ball, each micron ball Surface is built-up by smaller particle.
Embodiment 4
At room temperature, 2mmol sodium vanadate is dissolved in 8 mL distilled water, by 1mmol CaCl2It is dispersed to 8 In mL distilled water, under magnetic agitation effect, sodium vanadate solution is added dropwise to CaCl2In dispersion liquid, 10 min are stirred, with 1mol/L H2SO4Solution continues to stir 10 min after the pH value of reaction system is adjusted into 9, is transferred to 25mL hydro-thermal reaction afterwards 160 DEG C of h of hydro-thermal reaction 12 in insulating box are placed in kettle, after sealing, room temperature is cooled to after completion of the reaction, gained is precipitated 60 DEG C of dry 12h in baking oven are placed in after washing 5 times respectively with deionized water and absolute ethyl alcohol, obtain Ca2V2O7Material.XRD is composed Figure(Fig. 6)As a result it is Ca to show product2V2O7;Scanning electron microscope analysis shows the micron ball that the product is 1-1.5 μm, and micron ball is Assembled by a large amount of a diameter of 50-100nm nano particle.
Embodiment 5
At room temperature, 4mmol sodium vanadate is dissolved in 8 mL distilled water, 2mmol CaO is dispersed to 8 mL In distilled water, under magnetic agitation effect, sodium vanadate solution is added dropwise in CaO dispersion liquids, 10 min are stirred, with 1mol/L HNO3Solution continues to stir 10 min after the pH value of reaction system is adjusted into 10, is transferred to afterwards in 25 mL hydrothermal reaction kettle, 160 DEG C of h of hydro-thermal reaction 12 in insulating box are placed on after sealing, are cooled to room temperature after completion of the reaction, with deionized water and nothing Water-ethanol, which precipitates gained after washing 5 times respectively, is placed in 60 DEG C of vacuum drying 8h in baking oven, obtains product.XRD spectra(Fig. 7) As a result product and Ca are shown2V2O7Standard card matches;Scanning electron microscope analysis shows the micron ball that the product is 1.5-2 μm, Micron ball is assembled by a large amount of a diameter of 50-100nm nano particle.
Embodiment 6
At room temperature, 1mmol sodium vanadate is dissolved in 8 mL distilled water, by 0.5mmol CaCl2It is dissolved to In 5mL distilled water, under magnetic agitation effect, sodium vanadate solution is added dropwise to CaCl2In solution, 10 min are stirred, with 1mol/L HNO3Solution continues to stir 10 min after the pH value of reaction system is adjusted into 9, is transferred to 20 mL hydro-thermal reaction afterwards 160 DEG C of hydro-thermal reaction 12h in insulating box are placed in kettle, after sealing, room temperature is cooled to after completion of the reaction, uses deionized water And absolute ethyl alcohol centrifuges after washing 5 times respectively, is placed in baking oven in 80 DEG C of dry 12h, obtains Ca2V2O7Micron ball material Material.XRD test results show product and Ca2V2O7Standard card matches;Electronic Speculum point is scanned under larger enlargement ratio Analysis(Fig. 8)Show that product has micron spherical structure, the diameter of micron ball is about 1-1.5 μm, is observed that simultaneously:The micron Ball is assembled by a large amount of a diameter of 50-100nm nano particle.
Application Example 1
Will be according to Ca made from embodiment 12V2O7Sphere material carries out UV-Vis DRS(DRS)Test, is as a result shown in Fig. 9, abscissa is wavelength in figure, ordinate statement diffusing reflection rate.As can be seen from the figure:Calcium vanadate micron ball is in 450- There is an obvious absworption peak in the range of 230nm, show that calcium vanadate micron ball has stronger absorbability to ultraviolet light. It meanwhile the material has good stabilization, can make an addition in the polymeric materials such as rubber, plastics and textile material, play anti- Ultraviolet, anti-aging effect, while the fields such as photocatalysis, insoluble drug release, optics, electricity can also be applied to.

Claims (3)

1. a kind of preparation method of calcium vanadate sphere material, it is characterised in that comprise the following steps:
1. calcium chloride, calcium nitrate or calcium oxide and sodium vanadate are pressed into Ca:V mol ratios are 1:1 ~ 3 is configured to mixed solution, described The concentration of calcium chloride, calcium nitrate or calcium oxide is 0.01 ~ 1mol/L;
2. adjusting mixed solution pH as 9 ~ 10 using acid solution, stir and react 2 ~ 48h after 140 ~ 200 DEG C, obtain crude product Solution;
3. the solution of step 2. middle gained crude product is cooled into room temperature, and by gained washing of precipitate, drying, obtain calcium vanadate micron Ball material;A diameter of 0.5 ~ 2 μm of the micron ball, calcium vanadate chemical composition are Ca2V2O7, it is assembled by nano particle, had There is three-dimensional hierarchical structure.
2. the preparation method of calcium vanadate sphere material according to claim 1, it is characterised in that the nano particle A diameter of 50 ~ 100nm.
3. the preparation method of calcium vanadate sphere material according to claim 1, it is characterised in that step 2. described in acid For nitric acid, hydrochloric acid or sulfuric acid.
CN201610071846.3A 2016-02-02 2016-02-02 Calcium vanadate sphere material and its preparation method and application Expired - Fee Related CN105712401B (en)

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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
CN109553134B (en) * 2019-01-23 2021-02-02 陕西科技大学 Flower cluster-shaped calcium vanadate microsphere and preparation method 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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