CN104876272B - A kind of preparation method of Emission in Cubic MnO/ porous carbon composite - Google Patents
A kind of preparation method of Emission in Cubic MnO/ porous carbon composite Download PDFInfo
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- CN104876272B CN104876272B CN201510163795.2A CN201510163795A CN104876272B CN 104876272 B CN104876272 B CN 104876272B CN 201510163795 A CN201510163795 A CN 201510163795A CN 104876272 B CN104876272 B CN 104876272B
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Abstract
The invention discloses a kind of preparation method of Emission in Cubic MnO/ porous carbon composite, the method is presoma by the monocrystalline of formic acid manganese, is prepared with Emission in Cubic MnO/ porous carbon composite using the method for growth in situ.Specifically preparation method is：(1) formic acid manganese monocrystalline is prepared by hydro-thermal method with manganese salt, DMF, three kinds of raw materials of water；(2) formic acid manganese monocrystalline is calcined under 500 800 DEG C of degree of nitrogen or vacuum environment, obtain Emission in Cubic MnO/ porous carbon composite.The Emission in Cubic MnO/ porous carbon composite structure of present invention acquisition, morphology controllable, preparation process are mainly by controlling calcining heat, atmosphere and time, simple to operate, it is easy to continuous prodution.
Description
Technical field
The present invention relates to the preparation of composite, specifically a kind of system of Emission in Cubic MnO/ porous carbon composite
Standby, Emission in Cubic MnO/ porous carbon composite is mainly used as the catalyst of amylalcohol manufacture, GND, the system of ultracapacitor
Make, the drier of coating and varnish, feed adjuvant, trace-element fertilizer, it can also be used to medicine, welding, smelt, fabric is reduced
Printing and dyeing, grease are bleached.
Background technology
Manganese monoxide is most basic Mn oxide, is production electrolytic manganese, potassium permanganate, manganese carbonate, electrolytic manganese dioxide,
Manganese sulfate and the raw material of other manganese salts.Manganese monoxide is widely used in the industry-by-industry of name of the country economy.It can be used as manufacture amylalcohol
Catalyst, produce the drier of ferrite and coating and varnish, be also used for medicine, welding, smelt, feed, glass coloration,
Grease is bleached, oily paint pigment, ore floatation, pottery, battery, the every field such as ultracapacitor.
At present, the preparation method of manganese monoxide is a lot, is most commonly used that high temperature solid-state method, hydro-thermal method, coprecipitation etc..
High temperature solid-state method：Sucrose is added in solid phase reaction generally in reactant, reduction atmosphere can be provided, prevent one
Manganese oxide is become high oxidation state manganese oxide by remaining dioxygen oxidation, can form carbon coating on manganese monoxide surface again, improve one
The electrical conductivity of manganese oxide.But manganese monoxide purity prepared by high temperature solid-state method is low, carbon skewness is easy to fall off.
Hydro-thermal method：First manganese dioxide is prepared by hydro-thermal method, then height is carried out in reduction atmosphere or addition carbon source
Warm reduction prepares manganese monoxide.Variously-shaped manganese monoxide can also be prepared by changing reducing agent or adjusting hydrothermal condition.
But the manganese monoxide specific surface area for preparing is little.
Coprecipitation：Precipitating reagent is added in manganese salt solution, and filtration drying is calcined, you can obtain manganese monoxide.In addition exist
Different organic solvents are added when preparing deposit presoma, can control sedimentary pattern and size, when organic matter viscosity
When larger, crystal growth can be prevented, less crystal is generated, control grain size.But coprecipitation prepares manganese monoxide
Purity is low, and has secondary pollution.
Content of the invention
It is an object of the invention to provide a kind of preparation method of Emission in Cubic MnO/ porous carbon composite, the method is not using
Manganese source together, solvent and reaction temperature control growth formic acid manganese monocrystalline, and be presoma further with formic acid manganese monocrystal material
By, under growth in situ, different temperatures, different atmosphere, different time, calcining obtains the porous carbon/oxidation of structure, morphology controllable
Manganese composite construction.The structure of Emission in Cubic MnO/ porous carbon composite has certain with the structure of presoma formic acid manganese monocrystal material
Frame relations, be to realize the basis that Emission in Cubic MnO/ porous carbon composite structure is constructed.
The concrete technical scheme for realizing the object of the invention is：
A kind of preparation method of Emission in Cubic MnO/ porous carbon composite, the method include step in detail below：
ⅰ）The preparation of formic acid manganese monocrystalline presoma
Manganese salt, water and DMF are proportionally 1mol:6-8mL:6-9mL, addition quality are manganese salt mass fraction 3-8%
Cetyl trimethylammonium bromide surfactant after, stir 30 minutes uniform mix after proceed in reactor, at 140 DEG C
Solvent thermal reaction 72h in baking oven, pours in beaker after being cooled to room temperature, and is sealed with preservative film, stands 3-7 days, occurs
Colourless bulk crystals in a large number；Then filter, 80 DEG C of dryings 8 hours, obtain formic acid manganese monocrystalline presoma；
ⅱ）The preparation of Emission in Cubic MnO/ porous carbon composite
In nitrogen flow under 20-50ml/min or vacuum environment, by step）Obtained presoma 500 DEG C-
Calcining 4h in 800 DEG C of tube furnaces, after tube furnace is cooled to room temperature, obtains described Emission in Cubic MnO/ porous carbon composite；Its
In：
The manganese salt is the manganese chloride of divalence, the one kind in manganese sulfate, manganese acetate, manganese nitrate.
The present invention obtains structure, shape with formic acid manganese monocrystalline as presoma by once calcining in the case of Template-free method
The controlled Emission in Cubic MnO/ porous carbon composite of looks, with certain novelty；By controlling the structural frames of formic acid manganese monocrystalline
The control of the preparation of frame relational implementation Emission in Cubic MnO/ porous carbon composite has stronger theoretical foundation, and main by control
Calcining heat processed, the structure of atmosphere and time control material, pattern, with stronger operability.The present invention obtain cube
Phase MnO/ porous carbon composite structure, morphology controllable, preparation process is by controlling calcining heat, atmosphere and time, operation letter
Single, it is easy to continuous prodution.
Description of the drawings
Fig. 1 is the X-ray powder diffraction figure of embodiment of the present invention 1-4 gained composite；
Fig. 2 is the flying-spot microscope figure of 1 gained composite of the embodiment of the present invention.
Specific embodiment
The present invention is described in detail with reference to embodiment.
Embodiment 1
（1）The preparation of formic acid manganese monocrystalline presoma
Tetra- chloride hydrate manganese of 0.3g, 9ml water, 9mlDMF are mixed, is subsequently adding 0.018g cetyl trimethyl bromination
Ammonium surfactant, proceeds in 25ml reactor after stirring uniform mixing in 30 minutes, solvent thermal reaction in 140 DEG C of baking ovens
72h, pours in beaker after being cooled to room temperature, and is sealed with preservative film, stands 7 days, colourless bulk crystals in a large number occurs；So
After filter, 80 DEG C of dryings obtain final product formic acid manganese monocrystalline presoma for 8 hours.
（2）The preparation of Emission in Cubic MnO/ porous carbon composite
In nitrogen flow for, under 20ml/min or vacuum environment, inciting somebody to action（1）Obtained presoma is in 500 DEG C of tube furnaces
Calcining 4h, tube furnace just obtain black Emission in Cubic MnO/ porous carbon composite after being cooled to room temperature.
Morphology analysis are carried out to the Emission in Cubic MnO/ porous carbon composite of gained using the S-4800 of Hitachi, such as scheme
2.As can be seen that defining than more uniform cubic structure.
Embodiment 2
（1）The preparation of formic acid manganese monocrystalline presoma
Tetra- chloride hydrate manganese of 0.3g, 9ml water, 13.5mlDMF are mixed, is subsequently adding 0.024g cetyl trimethyl bromine
Change ammonium surfactant, proceed in 25ml reactor after stirring uniform mixing in 30 minutes, solvent thermal reaction in 140 DEG C of baking ovens
72h, pours in beaker after being cooled to room temperature, and is sealed with preservative film, stands 3 days, colourless bulk crystals in a large number occurs；So
After filter, 80 DEG C of dryings obtain final product formic acid manganese monocrystalline presoma for 8 hours.
（2）The preparation of Emission in Cubic MnO/ porous carbon composite
In nitrogen flow for, under 50ml/min or vacuum environment, inciting somebody to action（1）Obtained presoma is in 600 DEG C of tube furnaces
Calcining 4h, tube furnace just obtain black Emission in Cubic MnO/ porous carbon composite after being cooled to room temperature.
Embodiment 3
（1）The preparation of formic acid manganese monocrystalline presoma
Tetra- chloride hydrate manganese of 0.3g, 10.5ml water, 12mlDMF are mixed, is subsequently adding 0.018g cetyl trimethyl
Bromination ammonium surfactant, proceeds in 25ml reactor after stirring uniform mixing in 30 minutes, and in 140 DEG C of baking ovens, solvent heat is anti-
72h is answered, is poured in beaker after being cooled to room temperature, and is sealed with preservative film, 5 days are stood, colourless bulk crystals in a large number occur；
Then filter, 80 DEG C of dryings obtain final product formic acid manganese monocrystalline presoma for 8 hours.
（2）The preparation of Emission in Cubic MnO/ porous carbon composite
In nitrogen flow for, under 30ml/min or vacuum environment, inciting somebody to action（1）Obtained presoma is in 700 DEG C of tube furnaces
Calcining 4h, tube furnace just obtain black Emission in Cubic MnO/ porous carbon composite after being cooled to room temperature.
Embodiment 4
（1）The preparation of formic acid manganese monocrystalline presoma
By tetra- chloride hydrate manganese of 0.3g, 9ml water, 9mlDMF mix, and are subsequently adding 0.015g cetyl trimethyl bromine
Change ammonium surfactant, proceed in 25ml reactor after stirring uniform mixing in 30 minutes, solvent thermal reaction in 140 DEG C of baking ovens
72h, pours in beaker after being cooled to room temperature, and is sealed with preservative film, stands 7 days, colourless bulk crystals in a large number occurs；So
After filter, 80 DEG C of dryings obtain final product formic acid manganese monocrystalline presoma for 8 hours.
（2）The preparation of Emission in Cubic MnO/ porous carbon composite
In nitrogen flow for, under 30ml/min or vacuum environment, inciting somebody to action（1）Obtained presoma is in 800 DEG C of tube furnaces
Calcining 4h, tube furnace just obtain black Emission in Cubic MnO/ porous carbon composite after being cooled to room temperature.
Performance and sign are carried out to the above-mentioned Emission in Cubic MnO/ porous carbon for preparing：Penetrated using D/max 2200PC type X
Line diffractometer carries out structural analysis, and Fig. 1 is shown in by its XRD collection of illustrative plates, it can be seen that embodiment 1-4 has all prepared the MnO/ of Emission in Cubic
Porous carbon composite.
Claims (1)
1. a kind of preparation method of Emission in Cubic MnO/ porous carbon composite, it is characterised in that the method includes to walk in detail below
Suddenly：
ⅰ）The preparation of formic acid manganese monocrystalline presoma
Manganese salt, water and DMF are proportionally 1mol 6-8mL 6-9mL, quality are added for the ten of manganese salt mass fraction 3-8%
After six alkyl trimethyl ammonium bromide surfactants, proceed in reactor after stirring uniform mixing in 30 minutes, in 140 DEG C of baking ovens
Middle solvent thermal reaction 72h, pours in beaker after being cooled to room temperature, and is sealed with preservative film, stands 3-7 days, occurs a large amount of
Colourless bulk crystals；Then filter, 80 DEG C of dryings 8 hours, obtain formic acid manganese monocrystalline presoma；
ⅱ）The preparation of Emission in Cubic MnO/ porous carbon composite
In nitrogen flow under 20-50ml/min or vacuum environment, by step）Obtained presoma is at 500 DEG C -800 DEG C
Calcining 4h in tube furnace, after tube furnace is cooled to room temperature, obtains described Emission in Cubic MnO/ porous carbon composite；Wherein：
The manganese salt is the one kind in manganese chloride, manganese sulfate, manganese acetate and the manganese nitrate of divalence.
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| CN106981643B (en) * | 2017-05-23 | 2019-07-16 | 山东大学 | A kind of method that biogel carbonization prepares the double-deck carbon coating manganous oxide electrode material |
| CN107394183A (en) * | 2017-08-10 | 2017-11-24 | 安庆师范大学 | A kind of preparation method of MnO nanocrystalline composite materials of porous carbon coating and its application in lithium battery |
| CN108751335A (en) * | 2018-05-04 | 2018-11-06 | 中山大学 | A kind of method of antibiotic in light-Fenton-like system concerted catalysis oxidative degradation water environment |
| CN111014712B (en) * | 2019-12-18 | 2023-05-02 | 山东大学 | Co/MnO@C composite electromagnetic wave absorbing material and preparation method and application thereof |
| CN115331978A (en) * | 2022-09-02 | 2022-11-11 | 河北工业大学 | Preparation method and application of positive and negative electrode matching material of lithium ion hybrid capacitor |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102208610A (en) * | 2011-04-18 | 2011-10-05 | 北京工业大学 | Preparation method of carbon coated MnO cathode material |
| CN103050679A (en) * | 2012-12-26 | 2013-04-17 | 浙江工业大学 | Spherical hollow porous MnO/C composite material and application thereof |
| CN103769082A (en) * | 2014-01-08 | 2014-05-07 | 浙江大学 | Preparation method of carbon-supported active MnOx, product of method and application of product |
| CN104392849A (en) * | 2014-11-20 | 2015-03-04 | 中南大学 | Manganese dioxide/ con composite material preparing method |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102208610A (en) * | 2011-04-18 | 2011-10-05 | 北京工业大学 | Preparation method of carbon coated MnO cathode material |
| CN103050679A (en) * | 2012-12-26 | 2013-04-17 | 浙江工业大学 | Spherical hollow porous MnO/C composite material and application thereof |
| CN103769082A (en) * | 2014-01-08 | 2014-05-07 | 浙江大学 | Preparation method of carbon-supported active MnOx, product of method and application of product |
| CN104392849A (en) * | 2014-11-20 | 2015-03-04 | 中南大学 | Manganese dioxide/ con composite material preparing method |
Non-Patent Citations (1)
| Title |
|---|
| 微/纳米结构MnO负极材料的制备与储锂性能;刘雅敏等;《研究与设计电源技术》;20120531;第36卷(第5期);第639-642页 * |
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