The preparation method of alkali formula manganese oxide nanometer rod
Technical field
The present invention relates to a kind of preparation method of alkali formula manganese oxide nanometer rod.
Background technology
Alkali formula manganese oxide (MnOOH) is a kind of very important material, and it has crucial purposes in fields such as electrochemistry, battery, electrochromism.MnOOH can be used as the presoma of preparation Li-Mn-O spinel structure, Manganse Dioxide and other manganese and oxygen compound.Tradition upper body phase MnOOH generally can pass through electrochemical production.In recent years, also some bibliographical informations are arranged hydrothermal method, reverse micelle method prepare MnOOH.
Chinese patent literature CN101428860A discloses a kind of method for preparing high purity MnOOH, and this method is hydrothermal method, and it is to use MnO
2And Mn
3O
4As the reaction precursor body, earlier with MnO
2And Mn
3O
4After the mixing, add entry, reaction 0.5~60 hour is promptly down in room temperature~100 ℃.The deficiency of this method is: MnO
2And Mn
3O
4Solubleness is smaller in water, and solid state reaction is not too even, sneaks into impurity in the product easily, and has used 2 kinds of manganese sources, and its product does not have specific pattern yet.
2004 the 62nd the 24th phases of volume of chemistry journal disclose the document of a piece " reverse micelle method preparation and sign of MnOOH nanometer rod ", and the method in the document is to adopt the aqueous solution/CTAB/ propyl carbinol/heptane four components to form reversed phase micelle system and MnCl
2Making diameter is the MnOOH nanometer rod that 10nm, length are about 200nm.The deficiency of this method is: need reversed phase micelle as template, and need to adopt tensio-active agent.
Chinese patent literature CN101851008 A discloses a kind of method of the MnOOH of preparation nanometer rod, and it is that dinethylformamide carries out solvent thermal reaction and obtains the MnOOH nanometer rod with potassium permanganate and N.The deficiency of this method is: used organic reagent N, dinethylformamide has pollution as solvent and reductive agent to environment.
Summary of the invention
The object of the present invention is to provide a kind of template that need not, product purity height, size distribution are even, and technology is simple, and is easy and simple to handle, mild condition, and green non-pollution is suitable for the preparation method of the alkali formula manganese oxide nanometer rod of suitability for industrialized production.
The technical scheme that realizes the object of the invention is: a kind of preparation method of alkali formula manganese oxide nanometer rod, it is to carry out hydro-thermal reaction with potassium permanganate and polyvinylpyrrolidone to obtain alkali formula manganese oxide nanometer rod.
What have says so: according to 5: 1~1: 10 weight ratio polyvinylpyrrolidone and potassium permanganate are dissolved in the water, under 100 ℃~200 ℃ temperature, carry out hydro-thermal reaction 2h~24h, then reacted product is carried out solid-liquid separation, solid after separating with distilled water, dehydrated alcohol or washing with acetone successively, drying solid obtains alkali formula manganese oxide nanometer rod under 30 ℃~100 ℃ temperature at last.
The temperature of above-mentioned hydro-thermal reaction is 140 ℃~160 ℃.
The temperature of above-mentioned drying solid is 50 ℃~90 ℃.
The K value of described polyvinylpyrrolidone is 15~90.
The positively effect that the present invention has: (1) method of the present invention does not need the effect of template, but directly carries out hydro-thermal reaction with potassium permanganate and polyvinylpyrrolidone, finally obtains the alkali formula manganese oxide nanometer rod that size distribution is even, purity is high.(2) method mild condition of the present invention does not adopt organic reagent, but adopt toxicity very low not only as reductive agent but also as the polyvinylpyrrolidone of tensio-active agent, green non-pollution belongs to green synthesis process.(3) technology of the present invention is simple, and is easy and simple to handle, is suitable for suitability for industrialized production.(4) the alkali formula manganese oxide that makes of the present invention is applied to fields such as catalysis, environmental improvement, electrode materials, capacitance material especially.
Embodiment
(embodiment 1)
Take by weighing the potassium permanganate of 0.2g, it is dissolved in the distilled water of 15mL, the powdered K value that adds 0.4g under agitation condition is 30 polyvinylpyrrolidone, change mixed solution over to hydrothermal reaction kettle then, in confined conditions, make the temperature of reaction system rise to 160 ℃, under 160 ℃ temperature, carry out hydro-thermal reaction 16h by temperature controlling system control reaction system.This reaction also is a redox reaction, and principal product wherein is alkali formula manganese oxide (an alkali formula manganese oxide), and alkali formula manganese oxide is solid, and all the other products are dissolved in the liquid system.With the post reaction mixture naturally cooling, carry out solid-liquid separation by the mode or the filtering mode of centrifugation then, use distilled water and absolute ethanol washing solid more successively, solid after vacuum-drying washing under 80 ℃ the temperature is 2~3 hours at last, air pressure in the loft drier is 0.01~0.03MPa, obtaining diameter is 100nm~400nm, and length is 10 μ m~15 μ m alkali formula manganese oxide nanometer rod powders.
(embodiment 2~embodiment 5)
Each embodiment is substantially the same manner as Example 1, and difference sees Table 1.
Table 1
? |
Embodiment 1 |
Embodiment 2 |
Embodiment 3 |
Embodiment 4 |
Embodiment 5 |
Polyvinylpyrrolidone |
0.4g |
0.2g |
0.4g |
0.4g |
0.1g |
Potassium permanganate |
0.2g |
0.2g |
0.2g |
0.2g |
0.2g |
Temperature of reaction |
160℃ |
160℃ |
140℃ |
160℃ |
160℃ |
Reaction times |
16h |
16h |
16h |
12h |
16h |
Drying temperature |
80℃ |
60℃ |
70℃ |
90℃ |
50℃ |