CN101597086A - Method for preparing nano manganese dioxide with different crystal forms in low-temperature acid solution - Google Patents
Method for preparing nano manganese dioxide with different crystal forms in low-temperature acid solution Download PDFInfo
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- CN101597086A CN101597086A CNA2009101395892A CN200910139589A CN101597086A CN 101597086 A CN101597086 A CN 101597086A CN A2009101395892 A CNA2009101395892 A CN A2009101395892A CN 200910139589 A CN200910139589 A CN 200910139589A CN 101597086 A CN101597086 A CN 101597086A
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Abstract
The invention discloses a method for preparing nano manganese dioxide with different crystal forms in a low-temperature acid solution, which comprises the steps of mixing potassium permanganate with the acid solution, reacting at the temperature lower than 100 ℃, and then filtering, washing and drying precipitates to prepare the nano manganese dioxide with different crystal forms and different appearances. The invention adopts potassium permanganate and acid solution as raw materials, prepares delta type nano manganese dioxide or alpha type nano manganese dioxide of single crystal form under the condition of low temperature, has the characteristics of low cost, simple process, low requirement on equipment, mild reaction condition, stable product quality and the like, is suitable for large-scale industrial production, and can be widely applied to the preparation and application fields of nano manganese dioxide and relevant basic theoretical research thereof.
Description
Technical Field
The invention relates to a preparation method of nano manganese dioxide, in particular to a method for preparing nano manganese dioxide with different crystal forms and different appearances in an acid solution environment by using potassium permanganate as a raw material under the conditions of low temperature and normal pressure by utilizing a liquid-phase oxidation-reduction mechanism.
Background
Manganese dioxide is an important industrial raw material with excellent performance, low price and environmental protection. The nano manganese dioxide has ion exchange performance, molecular adsorption performance and excellent electrochemical performance, has more excellent performance due to high specific surface area and chemical activity, and is widely applied to the fields of environment-friendly materials, biosensors, zinc-manganese batteries, lithium ion batteries, super capacitor electrode materials and the like.
The crystal structure of manganese dioxide is complex, and the preparation method is also diversified. The conventional preparation of the nano manganese dioxide is mainly carried out by a hydrothermal method, but the reaction of the method needs to be carried out at high temperature and high pressure, so that the method has high requirements on equipment, long preparation period and high cost, and is not beneficial to large-scale production. And the liquid phase precipitation is used for preparing the nano manganese dioxide mostly in a mixed crystal form and with poor crystallinity by utilizing the principle of oxidation reduction at normal temperature and normal pressure. There are few reports on a method for preparing nano manganese dioxide by using a liquid-phase redox reaction under a low-temperature normal-pressure condition in an acid solution environment.
Disclosure of Invention
The invention aims to provide a method for preparing nano manganese dioxide with different crystal forms in a low-temperature acid solution, which aims to solve the problem that the prior art is difficult to adapt to industrial large-scale production.
The technical principle adopted by the invention is as follows:
reacting potassium permanganate as manganese source in acid solution at low temperature, controlling reaction temperature, acid concentration, reactant molar ratio, reaction time and other technological parameters, filtering, washing and drying the precipitate to prepare spherical delta-MnO 2 Or linear alpha-MnO 2 。
The technical scheme adopted by the invention is as follows: taking an acid solution with the concentration of 0.1-50 mol/L, and then measuring potassium permanganate according to the molar ratio of the potassium permanganate to the acid of 1: 1-1: 200 to prepare a potassium permanganate aqueous solution; mixing the potassium permanganate aqueous solution with the acid solution, reacting for 0.5-24 hours at normal temperature or below 100 ℃, and then filtering, washing and drying the precipitate to selectively prepare the flower-ball delta-type nano manganese dioxide or linear alpha-type nano manganese dioxide with single crystal form.
The acid is inorganic acid or organic acid.
The inorganic acid is hydrochloric acid, nitric acid or sulfuric acid.
The organic acid is acetic acid.
The invention adopts potassium permanganate and acid solution as raw materials, prepares delta type nano manganese dioxide or alpha type nano manganese dioxide of single crystal form under the condition of low temperature, has the characteristics of simple process, low cost, low requirement on equipment, mild reaction condition, stable product quality and the like, is suitable for large-scale industrial production, and can be widely applied to the preparation and application fields of nano manganese dioxide and relevant basic theory research thereof.
Drawings
FIG. 1 is a delta-MnO prepared in example 1 2 X-ray diffraction pattern.
FIG. 2 is delta-MnO prepared in example 1 2 Transmission electron micrograph.
FIG. 3 is a view of α -MnO prepared in example 2 2 X-ray diffraction pattern.
FIG. 4 is a graph obtained in example 2Prepared alpha-MnO 2 Transmission electron micrograph.
FIG. 5 is a delta-MnO prepared in example 5 2 Transmission electron micrograph.
FIG. 6 is α -MnO prepared in example 6 2 Transmission electron micrograph.
FIG. 7 is delta-MnO prepared in example 7 2 Transmission electron micrograph.
Detailed Description
The following examples are given to illustrate the present invention and it should be noted that the following examples are only for illustrative purposes and should not be construed as limiting the scope of the present invention, and that the non-essential modifications and adjustments made by those skilled in the art according to the above disclosure will still fall within the scope of the present invention.
Example one
This example uses potassium permanganate and hydrochloric acid as raw materials.
Weighing 5g of potassium permanganate, dissolving the potassium permanganate in a proper amount of distilled water, placing the potassium permanganate into a constant-temperature water bath heating pot, stirring, heating, keeping the constant temperature at 60 ℃, measuring 16g of hydrochloric acid, adding distilled water to dilute the hydrochloric acid to 1mol/L, slowly dropwise adding a potassium permanganate aqueous solution, reacting until the solution is clear, filtering with distilled water, washing and drying. The product is identified as delta-type nano manganese dioxide by X-ray diffraction analysis. Under the same conditions, the delta type nano manganese dioxide can be obtained at room temperature, 70 ℃, 80 ℃, 90 ℃ or with the hydrochloric acid concentration less than (excluding) 4mol/L, and the product crystallinity is slightly different according to the difference of the reaction temperature and the hydrochloric acid concentration.
Example two
This example uses potassium permanganate and hydrochloric acid as starting materials.
Weighing 5g of potassium permanganate, dissolving the potassium permanganate in a proper amount of distilled water, placing the potassium permanganate into a constant-temperature water bath heating pot, stirring, heating, keeping the constant temperature at 80 ℃, measuring 16g of hydrochloric acid, adding distilled water to dilute the hydrochloric acid to 4mol/L, slowly dropwise adding a potassium permanganate aqueous solution, reacting until the solution is clear, filtering and washing the solution with distilled water, and drying the solution to obtain brownish black powder. The product is identified as alpha type nano manganese dioxide by X-ray diffraction analysis. Under the same condition, the alpha-type nano manganese dioxide can be obtained at the reaction temperature of 85 ℃, 90 ℃, 95 ℃ or the hydrochloric acid concentration of not less than 4mol/L, and the length-diameter ratio of the product is slightly different according to the difference of the reaction temperature and the hydrochloric acid concentration.
EXAMPLE III
This example uses potassium permanganate and acetic acid as raw materials.
Weighing 60g of acetic acid, adding distilled water to dilute the acetic acid to 5mol/L, putting the mixture into a constant-temperature water bath heating pot, stirring, heating and keeping the constant temperature at 85 ℃, weighing 4g of potassium permanganate, dissolving the potassium permanganate in a proper amount of distilled water, slowly dropwise adding an acetic acid aqueous solution, reacting for 1.5 hours, filtering and washing the solution with distilled water, and drying the solution to obtain brownish black powder. The product is identified as delta type nano manganese dioxide by X-ray diffraction analysis. Under the same conditions, the reaction temperature is 75 ℃ and 95 ℃, delta type nano manganese dioxide can be obtained, and the crystallinity of the product is slightly different according to the difference of the reaction temperature and the acetic acid concentration.
Example four
This example uses potassium permanganate and acetic acid as raw materials.
Weighing 90g of acetic acid, adding distilled water to dilute the acetic acid to 10mol/L, putting the mixture into a constant-temperature water bath heating pot, stirring and heating the mixture to keep the constant temperature at 95 ℃, weighing 4g of potassium permanganate, dissolving the potassium permanganate in a proper amount of distilled water, slowly dropwise adding the acetic acid aqueous solution, reacting for 1.5 hours, filtering and washing the solution by using the distilled water, and drying the solution to obtain brownish black powder. The product is identified as alpha type nano manganese dioxide by X-ray diffraction analysis.
EXAMPLE five
This example uses potassium permanganate and sulfuric acid as starting materials.
Weighing 41g of sulfuric acid, adding distilled water to dilute the sulfuric acid to 2mol/L, placing the sulfuric acid into a constant-temperature water bath heating pot, stirring and heating to keep the constant temperature at 55 ℃, weighing 3g of potassium permanganate, dissolving the potassium permanganate in a proper amount of distilled water, slowly dropwise adding a sulfuric acid aqueous solution, reacting for 1 hour, filtering and washing the potassium permanganate with the distilled water, and drying the potassium permanganate to obtain brownish black powder. The product is identified as delta type nano manganese dioxide by X-ray diffraction analysis. Under the same conditions, the delta type nano manganese dioxide can be obtained at room temperature, 60 ℃, 70 ℃, 80 ℃ and 90 ℃ or at a sulfuric acid concentration of less than (not including) 4mol/L, and the product crystallinity is slightly different according to the difference of the reaction temperature and the sulfuric acid concentration.
EXAMPLE six
In this example, potassium permanganate and sulfuric acid were used as raw materials.
Weighing 44g of sulfuric acid, adding distilled water to dilute the sulfuric acid to 4mol/L, placing the sulfuric acid into a constant-temperature water bath heating pot, stirring, heating to keep the constant temperature at 95 ℃, weighing 3g of potassium permanganate, dissolving the potassium permanganate in a proper amount of distilled water, slowly dropwise adding a sulfuric acid aqueous solution, reacting for 1 hour, filtering and washing the potassium permanganate with distilled water, and drying to obtain brownish black powder. The product is identified as alpha type nano manganese dioxide by X-ray diffraction analysis.
EXAMPLE seven
This example uses potassium permanganate and nitric acid as starting materials.
Weighing 40g of nitric acid, adding distilled water to dilute the nitric acid to 2mol/L, putting the nitric acid into a constant-temperature water bath heating pot, stirring, heating and keeping the constant temperature at 70 ℃, weighing 3g of potassium permanganate, dissolving the potassium permanganate in a proper amount of distilled water, slowly dropwise adding a nitric acid aqueous solution, reacting for 1 hour, filtering and washing the potassium permanganate with the distilled water, and drying the potassium permanganate to obtain brownish black powder. The product is identified as delta type nano manganese dioxide by X-ray diffraction analysis. Under the same conditions, the delta type nano manganese dioxide can be obtained at the reaction temperature of room temperature, 65 ℃, 75 ℃, 80 ℃ and 90 ℃, and the crystallinity of the product is slightly different according to the difference of the reaction temperature and the concentration of nitric acid.
Example eight
In this example, potassium permanganate and nitric acid were used as raw materials.
Weighing 156g of nitric acid, adding distilled water to dilute the nitric acid to 8mol/L, putting the nitric acid into a constant-temperature water bath heating pot, stirring, heating and keeping the constant temperature at 90 ℃, weighing 3g of potassium permanganate, dissolving the potassium permanganate in a proper amount of distilled water, slowly dropwise adding a nitric acid aqueous solution, reacting for 1 hour, filtering and washing the potassium permanganate with the distilled water, and drying the potassium permanganate to obtain brownish black powder. The product is identified as alpha type nano manganese dioxide by X-ray diffraction analysis.
Claims (4)
1. A method for preparing nano manganese dioxide with different crystal forms in low-temperature acid solution is characterized in that: taking an acid solution with the concentration of 0.1-50 mol/L, and then taking potassium permanganate according to the molar ratio of 1: 1-1: 200 of the potassium permanganate to prepare a potassium permanganate aqueous solution; mixing the potassium permanganate aqueous solution with the acid solution, reacting for 0.5-24 hours at normal temperature or below 100 ℃, and then filtering, washing and drying the precipitate to selectively prepare the flower-ball delta-type nano manganese dioxide or linear alpha-type nano manganese dioxide with single crystal form.
2. The method for preparing nano manganese dioxide with different crystal forms in low-temperature acid solution according to claim 1, wherein the method comprises the following steps: the acid is inorganic acid or organic acid.
3. The method for preparing nano manganese dioxide with different crystal forms in low-temperature acid solution according to claim 1, wherein the method comprises the following steps: the inorganic acid is hydrochloric acid, nitric acid or sulfuric acid.
4. The method for preparing nano manganese dioxide with different crystal forms in low-temperature acid solution according to claim 1, wherein the method comprises the following steps: the organic acid is acetic acid.
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| CN102030371A (en) * | 2010-12-21 | 2011-04-27 | 北京化工大学 | Preparation method of manganese dioxide nanowire with high aspect ratio |
| CN102070196A (en) * | 2011-01-18 | 2011-05-25 | 浙江理工大学 | Method for preparing manganese dioxide nano rod at low temperature |
| CN102087921A (en) * | 2011-01-21 | 2011-06-08 | 清华大学 | Self-supporting super capacitor electrode material and preparation method thereof |
| CN102161511A (en) * | 2011-03-12 | 2011-08-24 | 广州市香港科大***研究院 | Preparation method of amorphous three-dimensional micro/nano-sized mesoporous manganese dioxide material used for electrochemical capacitor |
| CN102660770A (en) * | 2011-02-25 | 2012-09-12 | 大连理工大学 | Preparation method for ZnMn2O4 nanorod by using alpha-MnO2 nanorod template method |
| CN103840179A (en) * | 2014-02-27 | 2014-06-04 | 浙江大学 | Three-dimensional graphene-based combined electrode with MnO2 and Au nanoparticle-coating surface, and preparation method and applications thereof |
| CN103872308A (en) * | 2013-12-06 | 2014-06-18 | 天津赫维科技有限公司 | Preparation method of long-life 3V compound lithium manganese oxide |
| CN103872309A (en) * | 2013-12-14 | 2014-06-18 | 天津赫维科技有限公司 | Preparation method of similarly-spherical low-voltage compound lithium manganese oxide |
| CN105329947A (en) * | 2015-10-28 | 2016-02-17 | 上海大学 | Preparation method of nano-manganese oxide of flocculent structure |
| WO2016023399A1 (en) * | 2014-08-13 | 2016-02-18 | 江苏华东锂电技术研究院有限公司 | Negative electrode active material, preparation method therefor, and lithium-ion battery |
| CN106935416A (en) * | 2017-01-09 | 2017-07-07 | 广东工业大学 | A kind of starfish shape δ MnO2The preparation method of nanometer sheet/carbon fiber paper combination electrode material |
| CN107935047A (en) * | 2017-12-19 | 2018-04-20 | 广东医科大学 | A kind of control synthetic method of different-shape and the nano-manganese dioxide of size |
| CN109796048A (en) * | 2019-03-27 | 2019-05-24 | 中国人民解放军陆军工程大学 | A kind of control synthetic method of different crystal forms manganese dioxide |
| CN110104689A (en) * | 2019-03-27 | 2019-08-09 | 河南省人民医院 | A kind of hollow manganese dioxide nano particle and preparation method thereof |
| CN110416530A (en) * | 2019-06-21 | 2019-11-05 | 广东工业大学 | A kind of flower-shaped manganese dioxide/carbon composite material and preparation method and application |
| CN115092966A (en) * | 2022-07-04 | 2022-09-23 | 嘉应学院 | Mixed-phase MnO of three-dimensional lamellar structure for toluene catalytic combustion 2 Preparation method of (1) |
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2009
- 2009-06-26 CN CNA2009101395892A patent/CN101597086A/en active Pending
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| CN102030371B (en) * | 2010-12-21 | 2012-07-25 | 北京化工大学 | Preparation method of manganese dioxide nanowire with high aspect ratio |
| CN102030371A (en) * | 2010-12-21 | 2011-04-27 | 北京化工大学 | Preparation method of manganese dioxide nanowire with high aspect ratio |
| CN102070196A (en) * | 2011-01-18 | 2011-05-25 | 浙江理工大学 | Method for preparing manganese dioxide nano rod at low temperature |
| CN102087921A (en) * | 2011-01-21 | 2011-06-08 | 清华大学 | Self-supporting super capacitor electrode material and preparation method thereof |
| CN102087921B (en) * | 2011-01-21 | 2014-01-01 | 清华大学 | Self-supporting super capacitor electrode material and preparation method thereof |
| CN102660770A (en) * | 2011-02-25 | 2012-09-12 | 大连理工大学 | Preparation method for ZnMn2O4 nanorod by using alpha-MnO2 nanorod template method |
| CN102161511A (en) * | 2011-03-12 | 2011-08-24 | 广州市香港科大***研究院 | Preparation method of amorphous three-dimensional micro/nano-sized mesoporous manganese dioxide material used for electrochemical capacitor |
| CN103872308A (en) * | 2013-12-06 | 2014-06-18 | 天津赫维科技有限公司 | Preparation method of long-life 3V compound lithium manganese oxide |
| CN103872309A (en) * | 2013-12-14 | 2014-06-18 | 天津赫维科技有限公司 | Preparation method of similarly-spherical low-voltage compound lithium manganese oxide |
| CN103840179B (en) * | 2014-02-27 | 2015-12-30 | 浙江大学 | Surface coating MnO 2with three-dimensional grapheme based combined electrode, the preparation method and application of Au nano particle |
| CN103840179A (en) * | 2014-02-27 | 2014-06-04 | 浙江大学 | Three-dimensional graphene-based combined electrode with MnO2 and Au nanoparticle-coating surface, and preparation method and applications thereof |
| WO2016023399A1 (en) * | 2014-08-13 | 2016-02-18 | 江苏华东锂电技术研究院有限公司 | Negative electrode active material, preparation method therefor, and lithium-ion battery |
| CN105329947A (en) * | 2015-10-28 | 2016-02-17 | 上海大学 | Preparation method of nano-manganese oxide of flocculent structure |
| CN106935416A (en) * | 2017-01-09 | 2017-07-07 | 广东工业大学 | A kind of starfish shape δ MnO2The preparation method of nanometer sheet/carbon fiber paper combination electrode material |
| CN106935416B (en) * | 2017-01-09 | 2019-08-23 | 广东工业大学 | A kind of starfish shape δ-MnO2Nanometer sheet/carbon fiber paper combination electrode material preparation method |
| CN107935047A (en) * | 2017-12-19 | 2018-04-20 | 广东医科大学 | A kind of control synthetic method of different-shape and the nano-manganese dioxide of size |
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| CN110104689A (en) * | 2019-03-27 | 2019-08-09 | 河南省人民医院 | A kind of hollow manganese dioxide nano particle and preparation method thereof |
| CN110104689B (en) * | 2019-03-27 | 2021-08-13 | 河南省人民医院 | Hollow manganese dioxide nano-particles and preparation method thereof |
| CN110416530A (en) * | 2019-06-21 | 2019-11-05 | 广东工业大学 | A kind of flower-shaped manganese dioxide/carbon composite material and preparation method and application |
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