CN106115783B - A kind of preparation method of molybdic acid chromium micro Nano material - Google Patents
A kind of preparation method of molybdic acid chromium micro Nano material Download PDFInfo
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- CN106115783B CN106115783B CN201610489228.0A CN201610489228A CN106115783B CN 106115783 B CN106115783 B CN 106115783B CN 201610489228 A CN201610489228 A CN 201610489228A CN 106115783 B CN106115783 B CN 106115783B
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- C—CHEMISTRY; METALLURGY
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- C01G39/00—Compounds of molybdenum
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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Abstract
The invention belongs to functional material preparing technical fields, it is related to a kind of preparation method of molybdic acid chromium micro Nano material, by molybdic acid and chromic nitrate, it is dissolved in oxalic acid aqueous solution, water is evaporated in the condition for heating and stirring, and cross-linking reaction is carried out, then i.e. acquisition molybdic acid chromium micro Nano material is heat-treated in Muffle furnace.Present invention process is simple and easy to do, and purity is high, and impurity content is low, and product manufacturing cost is low, has excellent performance, can be with industrialized mass production.Molybdic acid chromium micro Nano material prepared by the present invention is used as negative thermal expansion material, is with a wide range of applications in space material, engine components and integrated circuit plate, optical device etc..
Description
Technical field
The invention belongs to the preparing technical fields of functional material, concretely relate to a kind of molybdic acid chromium micro Nano material
Preparation method.
Background technology
Most of materials all have behavior of expanding with heat and contract with cold in extraneous temperature change, but also have a few materials to have exception
Hot expansion property, volume reduce instead with the rise of ambient temperature, i.e. negative expansion behavior.The application of negative thermal expansion material
Field is very extensive, and low thermal expansion or coefficient of thermal expansion can be not only combined into conventional material close to zero refractory ceramics device
Part is applied in space material, engine components and integrated circuit plate, optical device etc., and sound, light, electricity,
Magnetic etc. also has a potential application value, therefore to the research of negative expansion performance materials by the concern of domestic and foreign scholars.
Molybdic acid chromium（Cr2（MoO4）3）It is a kind of important negative expansion performance materials, people surround it to molybdic acid chromium material
Crystal structure, negative dyeing technology, phase transition and thermophysical property etc. expand substantial amounts of research.But it is prepared
The research of method is less, is mainly prepared especially with chemical method to prepare molybdic acid chromium using sol-gal process.But still because
It is difficult to control for hydrolysis rate, and crystal shape is caused to be difficult to control, the defects of yield is low, and purity is not high.
The content of the invention
It is contemplated that low, the easily operated control that provides a kind of manufacturing cost in place of overcome the deficiencies in the prior art, instead
Answer temperature low, purpose product high income, homogeneity is good, the preparation method of the high molybdic acid chromium micro Nano material of purity.By multigroup
Contrast test finds that oxalic acid plays an important role in preparation process.Preparation method of the present invention can be applied equally to other work(
The chemical synthesis research of energy material, and have broad application prospects.
In order to achieve the above objectives, the present invention is realized in.
A kind of preparation method of molybdic acid chromium micro Nano material, molybdic acid and chromic nitrate are dissolved in oxalic acid aqueous solution, added
After heat and the condition stirred are evaporated water, cross-linking reaction is carried out, to get purpose product after the pyroreaction that continues.
As a preferred embodiment, the molar ratio of molybdic acid of the present invention, chromic nitrate and oxalic acid is followed successively by 3：2：30~60.
Further, the molar concentration of molybdic acid of the present invention is 0.01~0.2 mol/L.
Further, the molar concentration of oxalic acid of the present invention is 0.1~1.0 mol/L.
Further, in the condition of the present invention for heating and stirring, heating temperature is 100 DEG C, and mixing speed is
60~300 revs/min.
Further, for cross-linking reaction temperature of the present invention at 150~400 DEG C, cross-linking reaction time is 2~4 h.
Further, for pyroreaction temperature of the present invention at 500~600 DEG C, the reaction time is 4~8 h.
Compared with prior art, the present invention has following features.
（1）The present invention, which develops, prepares molybdic acid chromium micro Nano material new technology route, product size 0.5~1.0 μm it
Between.The technique manufacturing cost is low, easy to control, has higher production efficiency, can realize industrial mass production.
（2）Purpose product yield（99.0%~99.6%）, product purity height（99.5%~99.7%）Industry can be met should
With requirement of the field to micro materials.
（3）Purpose product molybdic acid chromium micro Nano material in UV-vis absorption spectrum, respectively 450 ± 10 nm,
There is stronger absworption peak at 600 ± 10 nm and 850 ± 10 nm tri-.
Description of the drawings
The invention will be further described with reference to the accompanying drawings and detailed description.Protection scope of the present invention not only office
It is limited to the statement of following content.
Fig. 1 is the molybdic acid chromium micro Nano material SEM figures of the present invention.
Fig. 2 is the molybdic acid chromium micro Nano material SEM figures of the present invention.
Fig. 3 is the molybdic acid chromium micro Nano material SEM figures of the present invention.
Fig. 4 is the molybdic acid chromium micro Nano material SEM figures of the present invention.
Fig. 5 is the molybdic acid chromium micro Nano material X-ray diffractogram of the present invention.
Fig. 6 is the molybdic acid chromium micro Nano material ultraviolet-visible spectrogram of the present invention.
Specific embodiment
The present invention designs a kind of chemical preparation process, and molybdic acid chromium micro Nano material is prepared by new chemistry route, this
Invention is dissolved in oxalic acid aqueous solution with molybdic acid and chromic nitrate, after the condition for heating and stirring is evaporated water, be crosslinked anti-
Should, to get purpose product after the pyroreaction that continues.Preparation process of the present invention is.
（1）Molybdic acid and chromic nitrate are dissolved in oxalic acid aqueous solution；The molar ratio of the molybdic acid, chromic nitrate and oxalic acid according to
Secondary is 3：2：30~60；The molar concentration of molybdic acid is 0.01~0.2 mol/L；The molar concentration of oxalic acid is 0.1~1.0 mol/
L。
（2）Mixed solution will be obtained after the condition for heating and stirring is evaporated water, carry out cross-linking reaction.Heating temperature is
100 DEG C, mixing speed is 60~300 revs/min；Cross-linking reaction temperature at 150~400 DEG C, cross-linking reaction time for 2~
4h。
（3）Cross-linking reaction terminates, then carries out high-temperature calcination, and pyroreaction temperature is at 500~600 DEG C, the reaction time 4
~8 h, temperature drop to room temperature to get purpose product.
（4）Prepared molybdic acid chromium micro Nano material is measured using UV, visible light sub-ray spectrometer in 190-900 nm ripples
Absorptivity in long scope.
Referring to shown in Fig. 1~4, scheme for the molybdic acid chromium micro Nano material SEM of the present invention, it can be seen that product is homogeneous to be distributed
The preferable micro Nano material of property.Fig. 5 is the molybdic acid chromium micro Nano material X-ray diffractogram of the present invention, and PDF card numbers are：20-0310.
Fig. 6 is the ultraviolet spectrogram of the molybdic acid chromium micro Nano material prepared by the present invention, respectively at 450nm, 600nm and 850nm tri-
There is stronger absworption peak.
Embodiment 1.
Molybdic acid, chromic nitrate and oxalic acid are made into aqueous solution, in 100 DEG C of heating, mixing speed is 300 revs/min of condition
Lower evaporation water.The molar ratio of wherein molybdic acid, chromic nitrate and oxalic acid is followed successively by 3：2：30.The molar concentration of molybdic acid is 0.05 mol/
L, the molar concentration of oxalic acid is 0.5 mol/L.After being evaporated water, cross-linking reaction is carried out, reaction temperature is in 200 DEG C, reaction time
2 it is small when, after cross-linking reaction, be connected in Muffle furnace and carry out pyroreaction, pyroreaction temperature is at 600 DEG C, the reaction time
For 4 h.To get to purpose product after natural cooling.Product size is 0.5 μm, and the yield of product is 99.1%；Product purity
99.5%, impurity content：Carbon is less than 0.5%；Product is in UV-vis absorption spectrum, respectively in 450 nm, 600 nm and 850
There is stronger absworption peak at nm tri-.
Embodiment 2.
Molybdic acid, chromic nitrate and oxalic acid are made into aqueous solution, in 100 DEG C of heating, under conditions of mixing speed is 60 revs/min
Evaporation water.The molar ratio of wherein molybdic acid, chromic nitrate and oxalic acid is followed successively by 3：2：60.The molar concentration of molybdic acid is 0.05 mol/L,
The molar concentration of oxalic acid is 0.5 mol/L.After being evaporated water, cross-linking reaction is carried out, reaction temperature is at 400 DEG C, the reaction time 2
Hour, it after cross-linking reaction, is connected in Muffle furnace and carries out pyroreaction, pyroreaction temperature is at 500 DEG C, the reaction time
For 8 h.To get to purpose product after natural cooling.Product size is 0.9 μm, and the yield of product is 99.6%；Product purity
99.7%, impurity content：Carbon is less than 0.3%；Product is in UV-vis absorption spectrum, respectively in 455 nm, 605 nm and 855
There is stronger absworption peak at nm tri-.
Embodiment 3.
Molybdic acid, chromic nitrate and oxalic acid are made into aqueous solution, in 100 DEG C of heating, mixing speed is 120 revs/min of condition
Lower evaporation water.The molar ratio of wherein molybdic acid, chromic nitrate and oxalic acid is followed successively by 3：2：50.The molar concentration of molybdic acid is 0.05 mol/
L, the molar concentration of oxalic acid is 0.5 mol/L.After being evaporated water, cross-linking reaction is carried out, reaction temperature is in 150 DEG C, reaction time
4 it is small when, after cross-linking reaction, be connected in Muffle furnace and carry out pyroreaction, pyroreaction temperature is at 600 DEG C, the reaction time
For 4 h.To get to purpose product after natural cooling.Product size is 0.5 μm, and the yield of product is 99.5%；Product purity
99.6%, impurity content：Carbon is less than 0.4%；Product is in UV-vis absorption spectrum, respectively in 455 nm, 602 nm and 850
There is stronger absworption peak at nm tri-.
Embodiment 4.
Molybdic acid, chromic nitrate and oxalic acid are made into aqueous solution, in 100 DEG C of heating, mixing speed is 200 revs/min of condition
Lower evaporation water.The molar ratio of wherein molybdic acid, chromic nitrate and oxalic acid is followed successively by 3：2：60.The molar concentration of molybdic acid is 0.1 mol/L,
The molar concentration of oxalic acid is 1.0 mol/L.After being evaporated water, cross-linking reaction is carried out, reaction temperature is at 200 DEG C, the reaction time 4
Hour, it after cross-linking reaction, is connected in Muffle furnace and carries out pyroreaction, pyroreaction temperature is at 600 DEG C, the reaction time
For 4 h.To get to purpose product after natural cooling.Product size is 1.0 μm, and the yield of product is 99.0%；Product purity
99.5%, impurity content：Carbon is less than 0.5%；Product is in UV-vis absorption spectrum, respectively in 455 nm, 610 nm and 860
There is stronger absworption peak at nm tri-.
Embodiment 5.
Molybdic acid, chromic nitrate and oxalic acid are made into aqueous solution, in 100 DEG C of heating, mixing speed is 300 revs/min of condition
Lower evaporation water.The molar ratio of wherein molybdic acid, chromic nitrate and oxalic acid is followed successively by 3：2：30.The molar concentration of molybdic acid is 0.1 mol/L,
The molar concentration of oxalic acid is 1.0 mol/L.After being evaporated water, cross-linking reaction is carried out, reaction temperature is at 200 DEG C, the reaction time 4
Hour, it after cross-linking reaction, is connected in Muffle furnace and carries out pyroreaction, pyroreaction temperature is at 600 DEG C, the reaction time
For 4 h.To get to purpose product after natural cooling.Product size is 0.7 μm, and the yield of product is 99.5%；Product purity
99.6%, impurity content：Carbon is less than 0.4%；Product is in UV-vis absorption spectrum, respectively in 440 nm, 590 nm and 845
There is stronger absworption peak at nm tri-.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., should all be included in the protection scope of the present invention.
Claims (5)
1. a kind of preparation method of molybdic acid chromium micro Nano material, which is characterized in that be made into molybdic acid, chromic nitrate and oxalic acid water-soluble
Liquid, in 100 DEG C of heating, mixing speed is evaporation water under conditions of 300 revs/min；Wherein mole of molybdic acid, chromic nitrate and oxalic acid
Than being followed successively by 3：2：30；The molar concentration of molybdic acid is 0.05 mol/L, and the molar concentration of oxalic acid is 0.5 mol/L；After being evaporated water,
Carry out cross-linking reaction, reaction temperature at 200 DEG C, the reaction time for 2 it is small when, after cross-linking reaction, be connected in Muffle furnace into
Row pyroreaction, for pyroreaction temperature at 600 DEG C, the reaction time is 4 h；To get to purpose product after natural cooling；Product
Size is 0.5 μm, and the yield of product is 99.1%；Product purity 99.5%, impurity content：Carbon is less than 0.5%；Product is ultraviolet
In visible absorption spectrum, there is stronger absworption peak at 450 nm, 600 nm and 850nm tri- respectively.
2. a kind of preparation method of molybdic acid chromium micro Nano material, which is characterized in that be made into molybdic acid, chromic nitrate and oxalic acid water-soluble
Liquid, in 100 DEG C of heating, mixing speed is evaporation water under conditions of 60 revs/min；Wherein mole of molybdic acid, chromic nitrate and oxalic acid
Than being followed successively by 3：2：60；The molar concentration of molybdic acid is 0.05 mol/L, and the molar concentration of oxalic acid is 0.5 mol/L；After being evaporated water,
Carry out cross-linking reaction, reaction temperature at 400 DEG C, the reaction time for 2 it is small when, after cross-linking reaction, be connected in Muffle furnace into
Row pyroreaction, for pyroreaction temperature at 500 DEG C, the reaction time is 8 h；To get to purpose product after natural cooling；Product
Size is 0.9 μm, and the yield of product is 99.6%；Product purity 99.7%, impurity content：Carbon is less than 0.3%；Product is ultraviolet
In visible absorption spectrum, there is stronger absworption peak at 455 nm, 605 nm and 855nm tri- respectively.
3. a kind of preparation method of molybdic acid chromium micro Nano material, which is characterized in that be made into molybdic acid, chromic nitrate and oxalic acid water-soluble
Liquid, in 100 DEG C of heating, mixing speed is evaporation water under conditions of 120 revs/min；Wherein mole of molybdic acid, chromic nitrate and oxalic acid
Than being followed successively by 3：2：50；The molar concentration of molybdic acid is 0.05 mol/L, and the molar concentration of oxalic acid is 0.5 mol/L；After being evaporated water,
Carry out cross-linking reaction, reaction temperature at 150 DEG C, the reaction time for 4 it is small when, after cross-linking reaction, be connected in Muffle furnace into
Row pyroreaction, for pyroreaction temperature at 600 DEG C, the reaction time is 4 h；To get to purpose product after natural cooling；Product
Size is 0.5 μm, and the yield of product is 99.5%；Product purity 99.6%, impurity content：Carbon is less than 0.4%；Product is ultraviolet
In visible absorption spectrum, there is stronger absworption peak at 455 nm, 602 nm and 850nm tri- respectively.
4. a kind of preparation method of molybdic acid chromium micro Nano material, which is characterized in that be made into molybdic acid, chromic nitrate and oxalic acid water-soluble
Liquid, in 100 DEG C of heating, mixing speed is evaporation water under conditions of 200 revs/min；Wherein mole of molybdic acid, chromic nitrate and oxalic acid
Than being followed successively by 3：2：60；The molar concentration of molybdic acid is 0.1 mol/L, and the molar concentration of oxalic acid is 1.0 mol/L；After being evaporated water,
Carry out cross-linking reaction, reaction temperature at 200 DEG C, the reaction time for 4 it is small when, after cross-linking reaction, be connected in Muffle furnace into
Row pyroreaction, for pyroreaction temperature at 600 DEG C, the reaction time is 4 h；To get to purpose product after natural cooling；Product
Size is 1.0 μm, and the yield of product is 99.0%；Product purity 99.5%, impurity content：Carbon is less than 0.5%；Product is ultraviolet
In visible absorption spectrum, there is stronger absworption peak at 455 nm, 610 nm and 860nm tri- respectively.
5. a kind of preparation method of molybdic acid chromium micro Nano material, which is characterized in that be made into molybdic acid, chromic nitrate and oxalic acid water-soluble
Liquid, in 100 DEG C of heating, mixing speed is evaporation water under conditions of 300 revs/min；Wherein mole of molybdic acid, chromic nitrate and oxalic acid
Than being followed successively by 3：2：30；The molar concentration of molybdic acid is 0.1 mol/L, and the molar concentration of oxalic acid is 1.0 mol/L；After being evaporated water,
Carry out cross-linking reaction, reaction temperature at 200 DEG C, the reaction time for 4 it is small when, after cross-linking reaction, be connected in Muffle furnace into
Row pyroreaction, for pyroreaction temperature at 600 DEG C, the reaction time is 4 h；To get to purpose product after natural cooling；Product
Size is 0.7 μm, and the yield of product is 99.5%；Product purity 99.6%, impurity content：Carbon is less than 0.4%；Product is ultraviolet
In visible absorption spectrum, there is stronger absworption peak at 440 nm, 590 nm and 845nm tri- respectively.
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