CN101700912B - Preparation method of silky nano-MnO2 - Google Patents
Preparation method of silky nano-MnO2 Download PDFInfo
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- CN101700912B CN101700912B CN2009103098759A CN200910309875A CN101700912B CN 101700912 B CN101700912 B CN 101700912B CN 2009103098759 A CN2009103098759 A CN 2009103098759A CN 200910309875 A CN200910309875 A CN 200910309875A CN 101700912 B CN101700912 B CN 101700912B
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Abstract
The invention relates to a preparation method of silky nano-MnO2 which aims to solve the technical problem that rod MnO2 with low length-diameter ratio can only be prepared by using the prior art, the preparation method of silky nano-MnO2 has complicated technology and high cost, etc. the technical scheme is characterized in that manganous salt is used as the manganese source, the ammonium nitrate is used as oxidant, the solution of manganous salt and the solution of ammonium nitrate are mixed evenly according to the molar ratio of 1:(60-100) to perform hydrothermal reaction for 1-8h at 170 DEG C and prepare silky nano-MnO2, then the product is filtrated to be separated, distilled water is used to wash the precipitate for 2-3 times and the finished product silky nano-MnO2 can be obtained by drying at 30-120 DEG C. the silky nano-MnO2 is prepared in the aqueous solution system so as to has the advantages of environmental friend, simple process flows and low production cost.
Description
Technical field
The present invention relates to a kind of preparation method of silky nano-MnO 2.
Background technology
Manganse Dioxide is a kind of material of very important battery, ultracapacitor and other electrochemical field, because preparation method's restriction, prepared nano level Manganse Dioxide mostly is particulate state, and the research worker wishes to prepare the silky nano-MnO 2 that specific surface is bigger and have the particular electrical chemical property very much.
The preparation silky nano-MnO 2 mainly adopts the alumina formwork method at present, and this method not only needs alumina formwork, and output is extremely low, and cost is very high, has seriously restricted the application of such nano material.Someone studied with manganous salt and potassium permanganate or manganous salt and persulphate etc. and prepared nano-manganese dioxide under hydrothermal condition, but generally can only prepare the little bar-shaped Manganse Dioxide of length-to-diameter ratio.
Summary of the invention
The object of the present invention is to provide that a kind of production technique is simple, with low cost, the preparation method of silky nano-MnO 2 with big L/D ratio.
The present invention solves the scheme that its technical problem adopts: be the manganese source with the manganous salt, with ammonium nitrate is oxygenant, with manganous salt solution and ammonium nitrate solution uniform mixing, wherein, the mol ratio of manganous salt and ammonium nitrate is 1: (60～100), regulator solution acidity pH value 1～2, under temperature condition more than 170 ℃, carried out hydro-thermal reaction 1～8 hour, generate silky nano-MnO 2, after separating after filtration again, precipitate 2～3 times with distilled water wash, drying promptly makes the silky nano-MnO 2 product under 30～120 ℃ of temperature.The concentration of described oxygenant ammonium nitrate is 8～12mol.dm
-3The preferred molar ratio of described manganous salt and ammonium nitrate is 1: (70～90).Described manganous salt comprises manganous nitrate, manganous sulfate, Manganous chloride tetrahydrate or manganous carbonate.Water-fast manganous salt adopts and comprises that hydrochloric acid or nitric acid dissolve, and described acid solutions is 0.1～1.0mol.dm
-3The acid of described regulator solution acidity comprises hydrochloric acid or nitric acid.Preferred 180 ℃～200 ℃ of described hydrothermal temperature.Preferred 2～7 hours of described hydro-thermal reaction time.Preferred 60～90 ℃ of described drying temperature.
The present invention has following characteristics:
(1) the present invention prepares silky nano-MnO 2 in water solution system, and is environmentally friendly.
(2) the present invention is without any need for template, adopts hydrothermal method just can prepare length and reaches tens microns, the silky nano-MnO 2 product of diameter tens nanometers.
(3) preparation technology of the present invention is simple, and cost is very cheap, accomplishes scale production easily.
The present invention not only production technique is simple, with low cost, and the product that adopts the inventive method to make is the silky nano-MnO 2 with big L/D ratio, can be applied to prepare battery, ultracapacitor, electrochemistry related device and inorganic/high polymer composite nano-material.
Description of drawings
Fig. 1 is that product of the present invention amplifies 40,000 times stereoscan photograph 1.
Fig. 2 is that product of the present invention amplifies 10,000 times stereoscan photograph 2.
Embodiment
The present invention is to be the manganese source with the manganous salt, and described manganous salt can adopt manganous nitrate, manganous sulfate, Manganous chloride tetrahydrate, manganese acetate or manganous carbonate etc., and described bivalent manganese strength of solution preferably is controlled at 0.05～0.5mol.dm
-3Between; And, can adopt acid such as hydrochloric acid, sulfuric acid or nitric acid to dissolve for water-fast manganous salt, the acid solutions of described dissolving usefulness preferably adopts 0.1～1.0mol.dm
-3Ammonium nitrate concn as oxygenant generally should be controlled at 8～12mol.dm
-3Between, preferably at 9～11mol.dm
-3Between, in this processing method, the concentration of ammonium nitrate or manganous salt is that influence synthesizes one of product very important factor.Is 1 with manganous salt solution and ammonium nitrate solution with mol ratio: the mixed of (60～100) is even, and the preferred molar ratio of described manganous salt and ammonium nitrate is 1: (70～90).Regulator solution acidity pH value 1～2 then, regulate preferably corresponding respectively hydrochloric acid, sulfuric acid or the nitric acid that adopts original dissolving usefulness of acid that acidity is used, preferably under 180-200 ℃ of temperature, carried out hydro-thermal reaction 1～8 hour, preferred 2～7 hours of described hydro-thermal reaction time, generate silky nano-MnO 2, after separating after filtration again, precipitate 2～3 times with distilled water wash, drying promptly makes the silky nano-MnO 2 product under 30～120 ℃ of temperature condition, preferably 60～90 ℃ of described drying temperatures.
Its concrete steps are:
(1) by a certain percentage manganous salt and ammonium nitrate are mixed with mixed aqueous solution.With acid-conditioning solution pH value is 1～2.
(2) change above-mentioned mixing solutions over to hydrothermal reaction kettle, temperature hydro-thermal reaction more than 170 ℃ 1～8 hour.
(3) filter to isolate precipitation, precipitate 2～3 times with distilled water wash.
(4) will be deposited in 30～120 ℃ of dryings down, obtain the silky nano-MnO 2 material.
Further specify embodiment and effect with following non-limiting formula embodiment.
Embodiment 1, and measuring compound concentration is 3.5mol.dm
-32 milliliters of manganese nitrate solutions, adding concentration is 10mol.dm
-355 milliliters in ammonium nitrate, be 0.5mol.dm with concentration
-3Nitric acid regulate pH to 1.2, change hydrothermal reaction kettle over to, 190 ℃ of reactions 5 hours down, be cooled to room temperature after, with sedimentation and filtration, with distilled water wash precipitation three times, after 50 ℃ of following dryings of temperature, product.
Embodiment 2, and measuring compound concentration is 3.5mol.dm
-32 milliliters of manganese nitrate solutions, adding concentration is 11mol.dm
-355 milliliters in ammonium nitrate, be 0.2mol.dm with concentration
-3Hydrochloric acid regulate pH to 1.5, change hydrothermal reaction kettle over to, 180 ℃ of reactions 2.0 hours down, be cooled to room temperature after, with sedimentation and filtration, with distilled water wash precipitation three times, after 80 ℃ of following dryings of temperature, product.
Embodiment 3, and measuring compound concentration is 3.5mol.dm
-32 milliliters of manganese sulfate solutions, adding concentration is 9mol.dm
-355 milliliters in ammonium nitrate, be 0.9mol.dm with concentration
-3Sulfuric acid regulate pH to 1.0, change hydrothermal reaction kettle over to, 180 ℃ of reactions 7 hours down, be cooled to room temperature after, with sedimentation and filtration, with distilled water wash precipitation three times, after 70 ℃ of following dryings of temperature, product.
Embodiment 4, and measuring compound concentration is 3.5mol.dm
-32 milliliters of manganese chloride solutions, adding concentration is 10mol.dm
-355 milliliters in ammonium nitrate, be 0.6mol.dm with concentration
-3Nitric acid regulate pH to 1.6, change hydrothermal reaction kettle over to, 200 ℃ of reactions 6 hours down, be cooled to room temperature after, with sedimentation and filtration, with distilled water wash precipitation three times, after 60 ℃ of following dryings of temperature, product.
Embodiment 5, and measuring compound concentration is 3.5mol.dm
-32 milliliters of manganese acetate solution, adding concentration is 9mol.dm
-355 milliliters in ammonium nitrate, be 0.8mol.dm with concentration
-3Sulfuric acid regulate pH to 1.6, change hydrothermal reaction kettle over to, 200 ℃ of reactions 7 hours down, be cooled to room temperature after, with sedimentation and filtration, with distilled water wash precipitation three times, after 60 ℃ of following dryings of temperature, product.
Embodiment 6, take by weighing a certain amount of manganous carbonate, use 0.5mol.dm
-3Behind the sulfuric acid dissolution, being made into concentration is 3.5mol.dm
-3Solution, measure 2 milliliters of this solution, adding concentration is 11mol.dm
-355 milliliters in ammonium nitrate, be 0.5mol.dm with concentration
-3Nitric acid regulate pH to 1.1, change hydrothermal reaction kettle over to, 190 ℃ of reactions 4 hours down, be cooled to room temperature after, with sedimentation and filtration, with distilled water wash precipitation three times, after 60 ℃ of following dryings of temperature, product.
The present invention prepares in water solution system, therefore have environmentally friendly, advantage such as technical process is simple, and preparation cost is cheap.
Claims (9)
1. the preparation method of a silky nano-MnO 2, it is characterized in that: be the manganese source with the manganous salt, with ammonium nitrate is oxygenant, with manganous salt solution and ammonium nitrate solution uniform mixing, wherein, the mol ratio of manganous salt and ammonium nitrate is 1: (60～100), regulator solution acidity pH value 1～2, under temperature condition more than 170 ℃, carried out hydro-thermal reaction 1～8 hour, generate silky nano-MnO 2, after separating after filtration, precipitate 2～3 times with distilled water wash, drying promptly makes the silky nano-MnO 2 product under 30～120 ℃ of temperature again.
2. according to the preparation method of the described silky nano-MnO 2 of claim 1, it is characterized in that: the concentration of described oxygenant ammonium nitrate is 8～12mol.dm
-3
3. according to the preparation method of the described silky nano-MnO 2 of claim 1, it is characterized in that: the mol ratio of described manganous salt and ammonium nitrate is 1: (70～90).
4. according to the preparation method of the described silky nano-MnO 2 of claim 1, it is characterized in that: described manganous salt comprises manganous nitrate, manganous sulfate, Manganous chloride tetrahydrate or manganous carbonate.
5. according to the preparation method of the described silky nano-MnO 2 of claim 1, it is characterized in that: water-fast manganous salt adopts and comprises that hydrochloric acid or nitric acid dissolve, and described acid solutions is 0.1～1.0mol.dm
-3
6. according to the preparation method of the described silky nano-MnO 2 of claim 1, it is characterized in that: the acid of described regulator solution acidity comprises hydrochloric acid or nitric acid.
7. according to the preparation method of the described silky nano-MnO 2 of claim 1, it is characterized in that: described hydrothermal temperature is 180 ℃～200 ℃.
8. according to the preparation method of the described silky nano-MnO 2 of claim 1, it is characterized in that: the described hydro-thermal reaction time is 2～7 hours.
9. according to the preparation method of the described silky nano-MnO 2 of claim 1, it is characterized in that: described drying temperature is 60～90 ℃.
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| KR101395361B1 (en) * | 2011-05-02 | 2014-05-14 | 삼성코닝정밀소재 주식회사 | Method of producing Manganese Oxide nano-wire |
| CN103021504B (en) * | 2012-11-10 | 2015-08-05 | 江苏瑞德新能源科技有限公司 | A kind of inorganic additive composition that can improve back electrode of solar cell adhesive force |
| CN107021525B (en) * | 2016-01-31 | 2018-04-24 | 湖南大学 | A kind of preparation method of high-purity birnessite type Mn oxide of efficient degradation of organic dye |
| CN105854871B (en) * | 2016-04-27 | 2019-03-29 | 广东工业大学 | A kind of preparation method and application of VOCs purified treatment catalyst |
| CN111514887A (en) * | 2020-04-28 | 2020-08-11 | 重庆工商大学 | α -MnO with exposed specific crystal face2Alpha crystal form metal oxide catalyst and preparation method thereof |
Citations (3)
| 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 |
| CN101428861A (en) * | 2008-12-15 | 2009-05-13 | 中国海洋石油总公司 | Process for producing high-purity manganese dioxide |
| CN101531402A (en) * | 2009-04-16 | 2009-09-16 | 上海交通大学 | Method for preparing manganese dioxide one-dimensional nanometer material |
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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 |
| CN101428861A (en) * | 2008-12-15 | 2009-05-13 | 中国海洋石油总公司 | Process for producing high-purity manganese dioxide |
| CN101531402A (en) * | 2009-04-16 | 2009-09-16 | 上海交通大学 | Method for preparing manganese dioxide one-dimensional nanometer material |
Non-Patent Citations (1)
| Title |
|---|
| Yi Liu, et al.A Simple Method of Fabricating Large-area α-MnO2 Nanowires and Nanorods.《Journal of Solid State Chemistry》.2006,第179卷(第6期),第1758页左栏第20行至第35行. * |
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