CN1312330C - 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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- CN1312330C CN1312330C CNB2004100208881A CN200410020888A CN1312330C CN 1312330 C CN1312330 C CN 1312330C CN B2004100208881 A CNB2004100208881 A CN B2004100208881A CN 200410020888 A CN200410020888 A CN 200410020888A CN 1312330 C CN1312330 C CN 1312330C
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- sulfuric acid
- manganese dioxide
- mno
- potassium permanganate
- acid solution
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- 239000002073 nanorod Substances 0.000 title claims abstract description 43
- 239000013078 crystal Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 64
- 238000000034 method Methods 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 229910003144 α-MnO2 Inorganic materials 0.000 abstract 2
- 239000000243 solution Substances 0.000 abstract 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 8
- 238000003917 TEM image Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005430 electron energy loss spectroscopy Methods 0.000 description 1
- 238000000619 electron energy-loss spectrum Methods 0.000 description 1
- 238000001889 high-resolution electron micrograph Methods 0.000 description 1
- 238000001239 high-resolution electron microscopy Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a preparation technology of manganese dioxide nano-rods, in particular to small-diameter alpha-MnO2A 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-MnO2(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, electrode materials in zinc-manganese 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. Therefore, researchers have prepared manganese dioxide nanostructures of different morphologies in different ways. Such as: mnO (MnO) 2 Nano-particlesParticle, 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 realize 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 adding amount of the potassium permanganate 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 drugs, 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 relatively uniform. 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. The manganese dioxide nanorod is 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 manganese dioxide nanorod [110] face 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 of 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 photo of manganese dioxide nanorods of example 3.
FIG. 3b is a high power scanning electron micrograph of the manganese dioxide nanorods of example 3 of the invention.
FIG. 3c is the TEM image of the manganese dioxide nanorods of example 3.
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. A transmission electron micrograph of the manganese dioxide nanorods shown in fig. 1 a. As shown in FIGS. 1b to 1c, the manganese dioxide obtained was alpha-MnO according to X-ray diffraction (XRD) and high resolution electron microscopy analysis 2 And (3) single crystal. As shown in fig. 1d, electron energy loss spectroscopy (EDS) indicated that the major elements of the product were oxygen and manganese.
Example 2
The difference from the example 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, and then adding deionized water to wash and dry. 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 embodiment 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 scanning electron microscope showed that the dioxide was oxidizedThe manganese nanorods are aggregated into particles with the diameter of 1-2 mu m, and the diameter of the manganese dioxide nanorods is about 4nm as shown by a scanning electron microscope. A transmission electron micrograph of the manganese dioxide nanorods 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 (2)
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 after the reaction is finished, naturally cooling to prepare uniform alpha-MnO with small diameter 2 Single crystal nanorods; the reaction temperature is 70-95 ℃; the concentration of the sulfuric acid solution is 0.1mol/l to 3mol/l, and the addition amount of potassium permanganate is 0.5 to 4g per 100 ml of sulfuric acid solution.
2. 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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| Application Number | Priority Date | Filing Date | Title |
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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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| CNB2004100208881A CN1312330C (en) | 2004-07-02 | 2004-07-02 | α－MnO 2 Preparation method of single crystal nanorod |
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| CN1715460A CN1715460A (en) | 2006-01-04 |
| CN1312330C true CN1312330C (en) | 2007-04-25 |
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Families Citing this family (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 |
| 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 |
| 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 |
| CN102336442B (en) * | 2011-06-30 | 2013-07-17 | 上海大学 | K0.125MnO2 nanowire and preparation method thereof |
| CN102583561B (en) * | 2012-01-12 | 2013-09-11 | 大连民族学院 | Alpha-phase manganese dioxide nano-rod, and preparation method and application thereof |
| 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 |
| CN107265504B (en) * | 2017-05-27 | 2019-04-16 | 安徽师范大学 | One-dimensional MnO2Nanotube and its preparation method and application |
| 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 |
| CN114212826B (en) * | 2021-11-23 | 2023-08-15 | 湖北大学 | Mo metal doped MnO 2 Electrode material, preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1377832A (en) * | 2002-01-18 | 2002-11-06 | 清华大学 | Process for synthesizing different crystal form one-dimensional single crystal mangnesium dioxide nano wire |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1377832A (en) * | 2002-01-18 | 2002-11-06 | 清华大学 | Process for synthesizing different crystal form one-dimensional single crystal mangnesium dioxide nano wire |
Non-Patent Citations (3)
| Title |
|---|
| BMNO2纳米棒的循环伏安行为研究 袁中直 周震涛等，精细化工，第21卷第2期 2004 * |
| 二氧化锰纳米微粒的制备及其共振瑞利散射光谱研究 陈飒，蒋治良，刘绍璞，西南师范大学学报(自然科学版)，第27卷第1期 2002 * |
| 纳米MnO2的制备及在超大容量电容器中的应用 闪星，张密林等，电源技术(研究与设计)，第26卷第2期 2002 * |
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