CN107416907A - A kind of preparation method of manganese oxide nanosphere - Google Patents
A kind of preparation method of manganese oxide nanosphere Download PDFInfo
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- CN107416907A CN107416907A CN201710861801.0A CN201710861801A CN107416907A CN 107416907 A CN107416907 A CN 107416907A CN 201710861801 A CN201710861801 A CN 201710861801A CN 107416907 A CN107416907 A CN 107416907A
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Abstract
The invention belongs to nano material synthesis and preparation field, and in particular to a kind of preparation method of manganese oxide nanosphere.CaSi is mixed by a certain percentage2Powder, Mg powder, Al powder, MnO2Powder, Mn powder and MgO powder, and the powder mixed is put into crucible and lighted in calm place with Laser Igniter.After powder combustion reaction terminates in crucible, windless condition is still maintained, target product (dust-like) descended slowly and lightly, settled naturally and is adsorbed in the nickel panel surface of crucible surrounding.Treat that the sedimentation of target complete product finishes, you can manganese oxide nanosphere attached to it is collected from nickel panel surface.Manganese oxide nanosphere is prepared using the inventive method, equipment investment is small, production efficiency is high, simple to operate, technology reproducibility is good, single batch output of production is high, process is environment friendly and pollution-free, gained manganese oxide nanosphere purity is high, best in quality, great commercial introduction value.
Description
Technical field
The invention belongs to nano material synthesis and preparation field, and in particular to a kind of preparation method of manganese oxide nanosphere.
Background technology
Mn oxide species is various, and the performance and purposes of various Mn oxides depend not only on Mn valence state also by its structure
Influence.Commonly referred manganese oxide refers to that chemical formula is MnO morexThe Mn oxide of (x is between 1 and 2), there is tunnel structure, it is main
To be used as the base of catalyst, adsorbent, sensor, wave absorbing agent, manganese oxide lithium primary cell, lithium ion cell positive, ion sieve etc.
Plinth raw material.The manganese oxide nanosphere of Nano grade is even more because small-size effect, quantum size effect, skin effect and maroscopic quantity
Sub- tunnel-effect and show many properties, such as more excellent electrochemical properties, catalytic capability, microwave absorbing property and absorption
Ability, and good surface modification, modification power.
At present, the synthesis of manganese oxide nanosphere mainly includes with preparation method：Chemical vapour deposition technique, hydro-thermal method, micro emulsion
Liquid method, sol-gal process, chemical deposition, electrochemical process, ball-milling method, microwave radiation technology emulsion method, masterplate method, solution combustion method,
Sonochemical method etc..Manganese oxide nanosphere purity height, good dispersion, even particle distribution made from these methods, and with excellent
Good chemical property, but preparation technology is complicated, require high to equipment or operating experience, single batch output of production is low, synthesis with
Long preparation period, and generally require to clean final product or intermediate product, a large amount of contaminative waste liquids are discharged, are rested on more
Laboratory is researched and developed or the small-scale low yield scale up test stage.Exactly early investment caused by these deficiencies is too high, produces effect
The problems such as rate is too low, technology reproducibility is poor, production cost is too high, waste gas and waste liquid is not disposable, causes prior art and is difficult to
Obtain industrial applications.Thus it is clear that in order to meet inexpensive, efficient, green modern industrialization large-scale production requirement, it is necessary to
It is proposed a kind of new manganese oxide nanosphere preparation method.
The content of the invention
The technical problems to be solved by the invention are the deficiency for existing manganese oxide nanosphere technology of preparing, there is provided
A kind of simple efficient, green and high product purity manganese oxide nanosphere preparation method.
Manganese oxide nanosphere preparation method provided by the invention, is achieved by the steps of：
Step (1), is respectively CaSi according to mass fraction2Powder 10.4-16.9 parts, Mg powder 4.2-12.5 parts, Al powder 9.5-
15.9 parts, MnO2Powder 46.3-58.7 parts, Mn powder 6.1-9.0 parts, the ratio of MgO powder 4.6-5.9 parts weigh CaSi2Powder, Mg powder, Al
Powder, MnO2Powder, Mn powder and MgO powder, and it is uniformly mixed, it is put into crucible；
Step (2), the crucible equipped with mixed-powder is placed in a nickel disk upper surface circle centre position；
Step (3), powder is lighted with Laser Igniter in calm place, is allowed to burn and reacts；
Step (4), after reaction terminates, windless condition is maintained, target product (dust-like) descended slowly and lightly, settled naturally and adsorb
In nickel panel surface；
Step (5), treat that the sedimentation of target complete product finishes, you can collect manganese oxide attached to it from nickel panel surface and receive
Rice ball.
Preferably, the CaSi2Powder, Mg powder, Al powder, MnO2The particle diameter of powder, Mn powder and MgO powder is 500-1000 mesh.
Preferably, 2.5-5 times of a diameter of crucible external diameter of the nickel disk..
Preferably, the crucible material is high purity graphite.
Preferably, obtained manganese oxide nanometer bulb diameter is distributed between about 40nm-719nm.
Preferably, the chemical formula of obtained manganese oxide nanosphere is MnOx(x=1.32-1.78).
A kind of manganese oxide nanosphere, is prepared using above-mentioned preparation method.
The chemical formula of gained manganese oxide nanosphere is MnOx(x=1.32-1.78), diameter is between about 40nm-719nm.
In the course of reaction, CaSi2Powder, Mg powder, Al powder and MnO2There occurs the acutely solid-state burning of complexity between powder
React and discharge amount of heat.Reaction product CaO, SiO2, MgO and Al2O3It is heated that partial melting occurs, and under gravity
Floating is gathered in reaction system surface, and the cellular for forming (discontinuous) off and on crushes skull.Reaction product Mn is together with original
Mn powder melted by heat in feed powder end, a part of Mn escape up reactant in gaseous form in the explosive vaporization of high-temperature fusant
System；And another part Mn be then full of in moment in crucible HTHP effect under, be extruded in liquid form it is spouting,
And when passing through inflated slag shell moment be atomized, reaction system is finally left in the form of microlayer model.Mn steams and the micro- liquid of Mn
Drop continues up rear natural subsidence in atmosphere after leaving reaction system, therebetween rapid cooling and fully oxidized, most end form
The nickel panel surface being attached into manganese oxide nanosphere around high purity graphite crucible.Involved related chemistry reacts：
2CaSi2+6Mg+4Al+11MnO2=2Al2O3+6MgO+4SiO2+2CaO+11Mn。
From MnO2As unique reducing agent, other metal simple-substances generation in addition to Mn is avoided, improves target product
Purity.
Product Al2O3, MgO, SiO2, CaO formed according to a certain percentage uniqueness solid-liquid two-phase skull, closing crucible outlet,
During so that product Mn not leaving crucible, in confined space, and there is larger pressure；When product Mn leaves crucible, skull
On liquid phase region broken through by Mn, formed micropore, turn into the passage that product Mn leaves crucible.
Nickel has good high-temperature stability, and carrying out target product (manganese oxide nanosphere) using nickel disk collects, Neng Gouyou
Effect avoids element pollution of the collection device to target product；Collection device is located at crucible bottom, is directly received not above crucible
Collect target product, but allow target product natural subsidence under no-wind environment this causes target product to exist on collection device
Holdup time in air greatly prolongs, and degree of oxidation is higher.
The major advantage and beneficial effect of method involved by the present invention are：Equipment investment is small, production efficiency is high, operation is simple
List, technology reproducibility are good, single batch output of production is high, process is environment friendly and pollution-free.Obtained manganese oxide nanosphere purity
Height, there is good electrochemical properties, adsorptivity, catalytic and wave absorbtion.
Brief description of the drawings
Fig. 1 is the side view of installation drawing used by preparation method of the present invention；
Fig. 2 is the top view of installation drawing used by preparation method of the present invention；
Fig. 3 is the electron scanning micrograph of the gained manganese oxide nanosphere of the embodiment of the present invention 2.
Reference：
1, nickel disk；2, material powder；3, graphite crucible.
Embodiment
It will be helpful to understand the present invention by the following description of the embodiments, but be not intended to limit present disclosure.
Embodiment 1
First, mass fraction is respectively 10.4%, 12.5%, 15.9%, 46.3%, 9.0% and 5.9% 500 are weighed
The CaSi of mesh size2Powder, Mg powder, Al powder, MnO2Powder, Mn powder and MgO powder, and it is uniformly mixed, gained material powder 2 is put
Enter in high purity graphite crucible 3.Then, high purity graphite crucible 3 is placed in the circle centre position of nickel disk 1 of a diameter of 5 times of crucible external diameters, such as schemed
Shown in 1,2.Finally, material powder 2 is lighted with Laser Igniter, is allowed to burn and reacts, and whole holding surrounding environment
In windless condition.After reaction terminates, windless condition is maintained, target product (dust-like) descended slowly and lightly, settled naturally and be adsorbed in
The surface of nickel disk 1.Treat that the sedimentation of target complete product finishes, you can the manganese oxide nanosphere attached to it from the surface collection of nickel disk 1.
TEM, SEM observation and XRD, EDS analysis are carried out to gained nanosphere, the results showed that：Gained manganese oxide nanosphere only contains Mn and O two
Kind element, purity is higher, chemical formula MnOx(x=1.32-1.69)；Nanometer bulb diameter is distributed between about 51nm-714nm.
Embodiment 2
First, 700 mesh that mass fraction is respectively 13.7%, 8.4%, 12.7%, 52.5%, 7.5% and 5.2% are weighed
The CaSi of size2Powder, Mg powder, Al powder, MnO2Powder, Mn powder and MgO powder, and it is uniformly mixed, gained material powder 2 is put into
In high purity graphite crucible 3.Then, high purity graphite crucible 3 is placed in the circle centre position of nickel disk 1 of a diameter of 3.5 times of crucible external diameters, such as schemed
Shown in 1,2.Finally, material powder 2 is lighted with Laser Igniter, is allowed to burn and reacts, and whole holding surrounding environment
In windless condition.After reaction terminates, windless condition is maintained, target product (dust-like) descended slowly and lightly, settled naturally and be adsorbed in
The surface of nickel disk 1.Treat that the sedimentation of target complete product finishes, you can the manganese oxide nanosphere attached to it from the surface collection of nickel disk 1.
TEM, SEM observation and XRD, EDS analysis are carried out to gained nanosphere, the results showed that：Gained manganese oxide nanosphere only contains Mn and O two
Kind element, purity is higher, chemical formula MnOx(x=1.39-1.78)；Nanometer bulb diameter is distributed between about 45nm-706nm,
As shown in Figure 3.
Embodiment 3
First, 1000 mesh that mass fraction is respectively 16.9%, 4.2%, 9.5%, 58.7%, 6.1% and 4.6% are weighed
The CaSi of size2Powder, Mg powder, Al powder, MnO2Powder, Mn powder and MgO powder, and it is uniformly mixed, gained material powder 2 is put into
In high purity graphite crucible 3.Then, high purity graphite crucible 3 is placed in the circle centre position of nickel disk 1 of a diameter of 2.5 times of crucible external diameters, such as schemed
Shown in 1,2.Finally, material powder 2 is lighted with Laser Igniter, is allowed to burn and reacts, and whole holding surrounding environment
In windless condition.After reaction terminates, windless condition is maintained, target product (dust-like) descended slowly and lightly, settled naturally and be adsorbed in
The surface of nickel disk 1.Treat that the sedimentation of target complete product finishes, you can the manganese oxide nanosphere attached to it from the surface collection of nickel disk 1.
TEM, SEM observation and XRD, EDS analysis are carried out to gained nanosphere, the results showed that：Gained manganese oxide nanosphere only contains Mn and O two
Kind element, purity is higher, chemical formula MnOx(x=1.36-1.71)；Nanometer bulb diameter is distributed between about 40nm-719nm.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (7)
1. a kind of preparation method of manganese oxide nanosphere, it is characterised in that comprise the following steps：
Step (1), is respectively CaSi according to mass fraction2Powder 10.4-16.9 parts, Mg powder 4.2-12.5 parts, Al powder 9.5-15.9
Part, MnO2Powder 46.3-58.7 parts, Mn powder 6.1-9.0 parts, the ratio of MgO powder 4.6-5.9 parts weigh CaSi2Powder, Mg powder, Al powder,
MnO2Powder, Mn powder and MgO powder, and it is uniformly mixed, it is put into crucible；
Step (2), the crucible equipped with mixed-powder is placed in a nickel disk upper surface circle centre position；
Step (3), powder is lighted with Laser Igniter in calm place, is allowed to burn and reacts；
Step (4), after reaction terminates, windless condition is maintained, target product descended slowly and lightly, settled naturally and is adsorbed in nickel panel surface；
Step (5), treat that the sedimentation of target complete product finishes, you can manganese oxide nanometer attached to it is collected from nickel panel surface
Ball.
2. the preparation method of manganese oxide nanosphere according to claim 1, it is characterised in that the CaSi2Powder, Mg powder, Al
Powder, MnO2The particle diameter of powder, Mn powder and MgO powder is 500-1000 mesh.
3. the preparation method of manganese oxide nanosphere according to claim 1, it is characterised in that the nickel disk is a diameter of described
2.5-5 times of crucible external diameter.
4. the preparation method of manganese oxide nanosphere according to claim 1, it is characterised in that the crucible material is high-purity
Graphite.
5. the preparation method of manganese oxide nanosphere according to claim 1, it is characterised in that obtained manganese oxide nanometer
Bulb diameter is distributed between 40nm-719nm.
6. the preparation method of manganese oxide nanosphere according to claim 1, it is characterised in that obtained manganese oxide nanometer
The chemical formula of ball is MnOx, wherein, x=1.32-1.78.
7. a kind of manganese oxide nanosphere, it is characterised in that prepared using the preparation method described in the claims any one of 1-6
Obtain.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110272718A (en) * | 2019-05-05 | 2019-09-24 | 安徽理工大学 | Al@MnO2Composite material, preparation method and application thereof |
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| CN102001700A (en) * | 2010-12-07 | 2011-04-06 | 武汉大学 | Method for synthesizing SnO2 nanoribbon by utilizing self-propagating high-temperature reaction |
| CN102874863A (en) * | 2012-10-24 | 2013-01-16 | 武汉大学 | Synthetic method for zinc oxide nano-particles |
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| CN101343081A (en) * | 2008-08-25 | 2009-01-14 | 陕西师范大学 | Method of preparing manganese oxide hollow nano-sphere with large-specific surface area |
| CN102001700A (en) * | 2010-12-07 | 2011-04-06 | 武汉大学 | Method for synthesizing SnO2 nanoribbon by utilizing self-propagating high-temperature reaction |
| CN102874863A (en) * | 2012-10-24 | 2013-01-16 | 武汉大学 | Synthetic method for zinc oxide nano-particles |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110272718A (en) * | 2019-05-05 | 2019-09-24 | 安徽理工大学 | Al@MnO2Composite material, preparation method and application thereof |
| CN110272718B (en) * | 2019-05-05 | 2022-05-13 | 安徽理工大学 | Al@MnO2Composite material, preparation method and application thereof |
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