CN1715460A - α－MnO 2 Preparation method of single crystal nanorod - Google Patents
α－MnO 2 Preparation method of single crystal nanorod Download PDFInfo
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- CN1715460A CN1715460A CN 200410020888 CN200410020888A CN1715460A CN 1715460 A CN1715460 A CN 1715460A CN 200410020888 CN200410020888 CN 200410020888 CN 200410020888 A CN200410020888 A CN 200410020888A CN 1715460 A CN1715460 A CN 1715460A
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Abstract
The invention relates to a preparation technology of manganese dioxide nano-rods, in particular to small-diameter alpha-MnO 2 A preparation method of single crystal nano rod. Potassium permanganate is added into sulfuric acid solution, and sulfuric acid and potassium permanganate react under heating condition at 70-95 deg.c. The diameter of the manganese dioxide nano-rod can be controlled by adjusting the concentration of the sulfuric acid solution, the addition amount of potassium permanganate, the temperature and other process parameters. The invention has the advantages of less chemical medicine types, simple process, convenient operation, easy control and no need of expensive equipment. The manganese dioxide being single-crystal alpha-MnO 2 (ii) a The manganese dioxide nano-rod has small diameter, short length, relatively uniform length and high specific surface area. The product prepared by the invention has wide application prospect, and can be used for catalysts, ion sieves, zinc and manganeseElectrode materials in batteries and lithium ion batteries, and the like.
Description
Technical Field
The invention relates to a preparation technology of manganese dioxide nano-rods, in particular to small-diameter alpha-MnO 2 A preparation method of single crystal nano rod.
Background
Due to the quantum size effect, the surface effect, the quantum tunneling effect and the like of the nano material, the nano material shows special properties which are not possessed by a plurality of conventional materials in the aspects of electricity, magnetism, sound, light, sensing, catalysis and the like. Therefore, it is receiving a wide attention.
Manganese oxide has excellent characteristics such as ion exchange, molecular adsorption, catalysis, electrochemistry, magnetism and the like, and is widely applied to catalysts, molecular sieves and supercapacitors. In addition, it has low cost, energy-neutral, and environmentally friendly properties as Li/MnO 2 Electrode material in a battery. In addition, the manganese dioxide has low price, rich resources and great application prospect and value.
The properties of manganese oxide are not only related to the valence state of manganese, but also depend on the morphological structure of manganese dioxide. Thus, researchers have prepared manganese dioxide nanostructures of different morphologies in different ways. Such as: mnO 2 Nanoparticles, alpha-, beta-, gamma-, delta-MnO 2 Nanowires and nanorods.
Disclosure of Invention
The invention aims to provide a method for preparing alpha-MnO with relatively simple operation 2 The method of the single crystal nano rod has simple process, does not need complex and expensive equipment, and is easy to control the reaction. Prepared alpha-MnO 2 The diameter of the single crystal nano rod is small and can reach 4nm.
In order to achieve the purpose, the technical scheme of the invention is as follows: adding potassium permanganate into a sulfuric acid solution, reacting sulfuric acid with the potassium permanganate under a heating condition, naturally cooling after the reaction is finished, adding deionized water, washing and drying. Wherein: the concentration of the sulfuric acid solution is 0.1mol/l to 3mol/l; the reaction temperature is 70-95 ℃. The diameter of the manganese dioxide nano-rod can be controlled by adjusting the concentration of the sulfuric acid solution, the addition amount of potassium permanganate, the temperature and other process parameters.
The potassium permanganate adding amount of the invention is preferably 0.5-4 g per 100 ml of sulfuric acid solution. The concentration of the sulfuric acid solution of the present invention is preferably 1 to 3M.
Compared with other methods for preparing the manganese dioxide nano-rod, the method has the following beneficial effects:
1. the process is simple. The invention adopts the method that only potassium permanganate is added into sulfuric acid solution and then alpha-MnO with smaller diameter and uniformity is prepared under the condition of heating 2 The single crystal nano rod needs few chemical medicine types, the reaction is simple and easy to control, expensive equipment is not needed, the operation is convenient, and the process is simple.
2. The manganese dioxide nano-rod has small diameter, short length and uniform length. The diameter range of the manganese dioxide nano-rod is as follows: 5-20nm, length range: 80-300nm.
3. The specific surface area of the nano rod is as high as 165.8m 2 /g。
4. Manganese dioxide nanorods being alpha-MnO 2 And (3) single crystal.
5. Has wide application prospect. The invention can be used for catalysts, ion sieves, electrode materials in zinc-manganese batteries and lithium ion batteries, and the like.
Drawings
FIG. 1a is a TEM image of manganese dioxide nanorods according to an embodiment 1 of the present invention.
FIG. 1b is a high resolution electron micrograph of the [110] surface of manganese dioxide nanorods of example 1 of the present invention.
FIG. 1c is an X-ray diffraction pattern (XRD) of manganese dioxide nanorods according to one embodiment 1 of the present invention.
FIG. 1d is an electron energy loss spectrum (EDS) of manganese dioxide nanorods according to one embodiment 1 of the present invention.
FIG. 2 is a TEM image of manganese dioxide nanorods according to example 2 of the present invention.
FIG. 3a is the SEM photograph of manganese dioxide nanorods according to example 3 of the present invention.
FIG. 3b is a high power scanning electron micrograph of manganese dioxide nanorods according to example 3 of the present invention.
FIG. 3c is the TEM image of the manganese dioxide nanorods of example 3 of the present invention.
FIG. 3d is the adsorption isotherm of manganese dioxide nanorods according to example 3 of the present invention.
Detailed Description
Example 1
Adding potassium permanganate into a sulfuric acid solution, wherein the concentration of the sulfuric acid solution is 3mol/l; adding 2g of potassium permanganate into every 100 ml of sulfuric acid solution; sulfuric acid and potassium permanganate were reacted under heating at a reaction temperature of 70 ℃. After the reaction is finished, naturally cooling, adding deionized water, washing and drying. The diameter of the manganese dioxide nano rod is about 20nm, and the length range is 80-150nm. The TEM image of the manganese dioxide nanorods is shown in FIG. 1 a. As shown in FIGS. 1b to 1c, manganese dioxide was obtained as alpha-MnO according to X-ray diffraction (XRD) and high resolution electron microscopy 2 And (3) single crystal. As shown in fig. 1d, electron energy loss spectroscopy (EDS) indicates that the major elements of the product are oxygen and manganese.
Example 2
The difference from the embodiment 1 is that:
adding potassium permanganate into a sulfuric acid solution, wherein the concentration of the sulfuric acid solution is 2mol/l; adding 1.5g of potassium permanganate into each 100 ml of sulfuric acid solution; the sulfuric acid and the potassium permanganate are reacted under the condition of heating, and the reaction temperature is 80 ℃. After the reaction is finished, naturally cooling, adding deionized water, washing and drying. 2. The diameter of the manganese oxide nanorod is about 8nm, the length of the manganese oxide nanorod ranges from 150nm to 200nm, and a transmission electron microscope photograph of the manganese dioxide nanorod is shown in figure 2.
Example 3
The difference from the example 1 is that:
potassium permanganate is added into a sulfuric acid solution, and the concentration of the sulfuric acid solution is 1mol/l; adding 2.5g of potassium permanganate into each 100 ml of sulfuric acid solution; the reaction was carried out under heating at a reaction temperature of 90 ℃. After the reaction is finished, naturally cooling, adding deionized water, washing and drying. As shown in FIGS. 3a to 3b, the TEM shows that the manganese dioxide nanorods are aggregated into particles of 1-2 μm, and the SEM shows that the diameter of the manganese dioxide nanorods is about 4nm. The TEM image of the manganese dioxide nanorods is shown in FIG. 3 c. As shown in FIG. 3d, the nitrogen adsorption isotherm of the manganese dioxide nanorods can be seen from the graph, and the manganese dioxide nanorods have a large external specific surface area and a strong capillary condensation phenomenon. This is due to the small diameter of the manganese dioxide nanorods and the agglomeration thereof. The specific surface area of the manganese dioxide nano-rod with small diameter is as high as 165.8m 2 /g。
Claims (4)
1. alpha-MnO 2 The preparation method of the single crystal nanorod is characterized by comprising the following steps: adding potassium permanganate into sulfuric acid solution, reacting sulfuric acid with potassium permanganate under heating condition, and cooling to obtain uniform alpha-MnO with small diameter 2 A single crystal nanorod.
2. The α -MnO of claim 1 2 The preparation method of the single crystal nanorod is characterized by comprising the following steps: the reaction temperature is 70-95 ℃.
3. The α -MnO of claim 1 2 The preparation method of the single crystal nanorod is characterized by comprising the following steps: concentration of the sulfuric acid solutionThe degree is 0.1mol/l to 3mol/l.
4. The α -MnO of claim 1 2 The preparation method of the single crystal nanorod is characterized by comprising the following steps: and adding deionized water into the obtained nano rod, washing and drying.
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| CNB2004100208881A CN1312330C (en) | 2004-07-02 | 2004-07-02 | α－MnO 2 Preparation method of single crystal nanorod |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100347345C (en) * | 2006-02-20 | 2007-11-07 | 浙江大学 | Method for preparing multi-branched hydroxy manganese oxide single crystal nanometer flower |
| CN101372363B (en) * | 2008-09-26 | 2011-07-20 | 中国科学院电工研究所 | Synthetic alpha-MnO 2 Method for micron hollow sphere and nanocluster |
| 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 |
| CN102336442A (en) * | 2011-06-30 | 2012-02-01 | 上海大学 | K0.125MnO2 nanowire and preparation method thereof |
| WO2012083511A1 (en) * | 2010-12-20 | 2012-06-28 | 海洋王照明科技股份有限公司 | Preparation method and use of manganese dioxide nano-rod |
| CN102583561A (en) * | 2012-01-12 | 2012-07-18 | 大连民族学院 | Alpha-phase manganese dioxide nano-rod, and preparation method and application thereof |
| CN103399040A (en) * | 2013-07-17 | 2013-11-20 | 武汉工程大学 | Gas-sensitive material for detecting acetaldehyde and method for producing gas-sensitive component by utilizing gas-sensitive material |
| CN107265504A (en) * | 2017-05-27 | 2017-10-20 | 安徽师范大学 | One-dimensional MnO2Nanotube and its preparation method and application |
| CN113426439A (en) * | 2021-06-02 | 2021-09-24 | 中山大学 | alpha-MnO with high specific surface area2Nano-rod and preparation method and application thereof |
| CN114212826A (en) * | 2021-11-23 | 2022-03-22 | 湖北大学 | MnO doped with Mo metal2Electrode material and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1142103C (en) * | 2002-01-18 | 2004-03-17 | 清华大学 | Process for synthesizing different crystal form one-dimensional single crystal mangnesium dioxide nano wire |
-
2004
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100347345C (en) * | 2006-02-20 | 2007-11-07 | 浙江大学 | Method for preparing multi-branched hydroxy manganese oxide single crystal nanometer flower |
| CN101372363B (en) * | 2008-09-26 | 2011-07-20 | 中国科学院电工研究所 | Synthetic alpha-MnO 2 Method for micron hollow sphere and nanocluster |
| CN103153870B (en) * | 2010-12-20 | 2015-04-15 | 海洋王照明科技股份有限公司 | Preparation method and use of manganese dioxide nano-rod |
| WO2012083511A1 (en) * | 2010-12-20 | 2012-06-28 | 海洋王照明科技股份有限公司 | Preparation method and use of manganese dioxide nano-rod |
| CN103153870A (en) * | 2010-12-20 | 2013-06-12 | 海洋王照明科技股份有限公司 | Preparation method and use of manganese dioxide nano-rod |
| 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 |
| CN102336442A (en) * | 2011-06-30 | 2012-02-01 | 上海大学 | K0.125MnO2 nanowire and preparation method thereof |
| CN102336442B (en) * | 2011-06-30 | 2013-07-17 | 上海大学 | K0.125MnO2 nanowire and preparation method thereof |
| CN102583561A (en) * | 2012-01-12 | 2012-07-18 | 大连民族学院 | Alpha-phase manganese dioxide nano-rod, and preparation method and application thereof |
| CN103399040A (en) * | 2013-07-17 | 2013-11-20 | 武汉工程大学 | Gas-sensitive material for detecting acetaldehyde and method for producing gas-sensitive component by utilizing gas-sensitive material |
| CN103399040B (en) * | 2013-07-17 | 2015-05-06 | 武汉工程大学 | Gas-sensitive material for detecting acetaldehyde and method for producing gas-sensitive component by utilizing gas-sensitive material |
| CN107265504A (en) * | 2017-05-27 | 2017-10-20 | 安徽师范大学 | One-dimensional MnO2Nanotube and its preparation method and application |
| CN107265504B (en) * | 2017-05-27 | 2019-04-16 | 安徽师范大学 | One-dimensional MnO2Nanotube and its preparation method and application |
| CN113426439A (en) * | 2021-06-02 | 2021-09-24 | 中山大学 | alpha-MnO with high specific surface area2Nano-rod and preparation method and application thereof |
| CN113426439B (en) * | 2021-06-02 | 2022-07-29 | 中山大学 | alpha-MnO with high specific surface area 2 Nano-rod and preparation method and application thereof |
| CN114212826A (en) * | 2021-11-23 | 2022-03-22 | 湖北大学 | MnO doped with Mo metal2Electrode material and preparation method and application thereof |
| CN114212826B (en) * | 2021-11-23 | 2023-08-15 | 湖北大学 | Mo metal doped MnO 2 Electrode material, preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1312330C (en) | 2007-04-25 |
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