CN103373744A - Preparation method of manganese dioxide nanorod - Google Patents
Preparation method of manganese dioxide nanorod Download PDFInfo
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- CN103373744A CN103373744A CN2012101238145A CN201210123814A CN103373744A CN 103373744 A CN103373744 A CN 103373744A CN 2012101238145 A CN2012101238145 A CN 2012101238145A CN 201210123814 A CN201210123814 A CN 201210123814A CN 103373744 A CN103373744 A CN 103373744A
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Abstract
The invention relates to a preparation method of manganese dioxide nanorod. The preparation method comprises the steps of: (1) blending manganese salt and alcohol water solution into mixed solution, wherein the solubility of the manganese slat in alcohol is greater than 0.005mg/L and less than 1mg/L; (2) adding an oxidant into the mixed solution to obtain a black solution, and standing still for 1-30 minutes; (3) under the condition of mechanical stirring or ultrasonic oscillation, adding a proper amount of water or diluted acid solution into the black solution, and gradually separating out black precipitates which are even in particle size; and (4) conducting centrifugal separation on the black precipitates, washing with water, and drying at 120DEG C to obtain the manganese dioxide nanorod.
Description
Technical field
The present invention relates to the preparation of manganese dioxide nano-rod.
Background technology
Manganse Dioxide is to study comparatively widely multi-functional transition metal oxide, and it has the advantages such as environmental friendliness, cheap, aboundresources, and has excellent physics and chemistry performance.Because its pattern polymorphism and rich (such as crystal formations such as α, β, Y) of crystalline structure, often being used in catalysis, ion-exchange, molecular sieve adsorption, biosensor, battery electrode material and energy storage can the field.
In recent years, nano-manganese dioxide particularly one dimension manganese dioxide nano structure such as nanoneedle, nanometer rod, nano wire, nanotube etc. owing to unique optics, electricity, magnetics and mechanical property receive much concern.How by starting material with low cost, the preparation technology of environmental friendliness simple possible prepares 1-dimention nano Manganse Dioxide and is significant.
The present preparation method of monodimension nanometer material mainly contains hydro-thermal, backflow, collosol and gel, liquid-phase precipitation, ultrasonic, electrochemical deposition etc.The shortcomings such as but they have oxidant cost height, temperature of reaction height, long reaction time, experimental implementation is complicated, energy consumption is large have limited its suitability for industrialized production.Chinese patent 201010221314.6 is used KBrO
3And MnSO
4Be raw material, adopt the microwave hydrothermal technology synthetic, because this invention is synthetic under hydrothermal condition, so that synthesis condition is complicated, and synthetic particle diameter is more greatly between 1 to 2 micron.Chinese patent 200910031024.2 utilizes Manganous chloride tetrahydrate and Virahol to be made into mixing solutions, adds the Manganse Dioxide that potassium permanganate obtains nanometer again, and oxidant potassium permanganate is expensive, has greatly increased synthetic cost.Minki Jo, Young-Ki Lee etc. are take ammonium persulphate as oxygenant, and manganous sulfate is raw material, in autoclave, make nano level Manganse Dioxide (Minki Jo, Young-Ki Lee, Kwang Man Kim, et al.Nanoparticle-Nanorod Core-Shell LiNi
0.5Mn
1.5O
4Spinel Cathodes with High Energy Density for Li-lon Batteries[J] .J.Electrochem.Soc.2010,157 (7): 841-845), the use of oxygenant ammonium persulphate has increased cost and easily to environment, the use of reactor has increased the cost on the production technique.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of manganese dioxide nano-rod.
The present invention is a kind of preparation method of manganese dioxide nano-rod, the steps include:
(1) manganese salt and alcohol solution are made into mixing solutions, used manganese salt for solubleness in alcohol is: greater than 0.005g/mL, less than 1g/mL;
(2) in mixing solutions, add oxygenant, obtain dark solution, left standstill 1～30 minute;
(3) under mechanical stirring or sonic oscillation condition, in dark solution, add suitable quantity of water, perhaps dilute acid soln, the gradually uniform black precipitate of precipitate particle;
(4) with the black precipitate centrifugation, and water washs, and is drying to obtain manganese dioxide nano-rod under 120 ℃.
Oxygenant of the present invention is some weak oxygenants, and is such as oxygen, hypochlorous acid, hydrogen peroxide etc., cheap and environmental pollution is little; Synthetic required equipment is simple, need not high-temperature and high-pressure conditions; The time of finishing whole technical process is very short, less than 1h.
Description of drawings
Fig. 1 is the transmission electron microscope picture of embodiment one gained manganese dioxide nano-rod, and Fig. 2 is the XRD spectra of gained nano-manganese dioxide in the invention process case one; The transmission electron microscope picture of the manganese dioxide nano-rod of Fig. 3 embodiment two gained; The transmission electron microscope picture of the manganese dioxide nano-rod of Fig. 4 embodiment three gained; The transmission electron microscope picture of the manganese dioxide nano-rod of Fig. 5 embodiment four gained.
Embodiment
The present invention is a kind of preparation method of manganese dioxide nano-rod, the steps include:
(1) manganese salt and alcohol solution are made into mixing solutions, used manganese salt for solubleness in alcohol is: greater than 0.005g/mL, less than 1g/mL;
(2) in mixing solutions, add oxygenant, obtain dark solution, left standstill 1～30 minute;
(3) under mechanical stirring or sonic oscillation condition, in dark solution, add suitable quantity of water, perhaps dilute acid soln, the gradually uniform black precipitate of precipitate particle;
(4) with the black precipitate centrifugation, and water washs, and is drying to obtain manganese dioxide nano-rod under 120 ℃.
Below in conjunction with embodiment technical scheme of the present invention is described further.
Embodiment one, and the preparation method of manganese dioxide nano-rod of the present invention the steps include:
(1) takes by weighing Mn (CH
3COO)
24H
2O 1.0g and 30mL dehydrated alcohol mixing wiring solution-forming;
(2) in step 1 gained solution, drip 2mL 30%H
2O
2, leave standstill 10min;
(3) under agitation condition, in step 2, slowly add 80mL distilled water, this moment can be in the dark solution the uniform black precipitate of precipitate particle gradually.
(4) centrifugal, the washing of the black precipitate that step 3 is obtained, 120 ℃ of spraying dryings namely get manganese dioxide nano-rod.
As shown in Figure 1, the diameter of the manganese dioxide nano-rod that obtains is 20～25nm, and length is 200～350nm.As shown in Figure 2, be the XRD spectra of gained nano-manganese dioxide.
Embodiment two, and the preparation method of manganese dioxide nano-rod of the present invention the steps include:
(1) takes by weighing Mn (CH
3COO)
24H
2O 1.5g and 30mL dehydrated alcohol mixing wiring solution-forming;
(2) in step 1 gained solution, drip 3mL 30%H
2O
2, leave standstill 15min;
(3) under agitation condition, in step 2, slowly add 80mL distilled water, this moment can be in the dark solution the uniform black precipitate of precipitate particle gradually.
(4) centrifugal, the washing of the black precipitate that step 3 is obtained, 120 ℃ of spraying dryings namely get manganese dioxide nano-rod.
As shown in Figure 3, the manganese dioxide nano-rod diameter that obtains is 20～30nm, and length is 200～300nm.
Embodiment three, and the preparation method of manganese dioxide nano-rod of the present invention the steps include:
(1) takes by weighing Mn (CH
3COO)
24H
2O 2.0g and 50mL anhydrous methanol mixing wiring solution-forming;
(2) in step 1 gained solution, drip 4mL 30%H
2O
2, leave standstill 20min;
(3) under agitation condition, in step 2, slowly add 100mL distilled water, this moment can be in the dark solution the uniform black precipitate of precipitate particle gradually.
(4) centrifugal, the washing of the black precipitate that step 3 is obtained, 120 ℃ of spraying dryings namely get manganese dioxide nano-rod.
As shown in Figure 4, the diameter of the manganese dioxide nano-rod that obtains is 20～25nm, and length is 150～200nm.
Embodiment four, and the preparation method of manganese dioxide nano-rod of the present invention the steps include:
(1) takes by weighing Mn (CH
3COO)
24H
2O 2.5g and 50mL anhydrous methanol mixing wiring solution-forming;
(2) in step 1 gained solution, drip 5mL 30%H
2O
2, leave standstill 25min;
(3) under agitation condition, slowly add 120mL distilled water in the described solution of step 2, this moment can be in the dark solution the uniform black precipitate of precipitate particle gradually.
(4) centrifugal, the washing of the black precipitate that step 3 is obtained, 120 ℃ of spraying dryings namely get manganese dioxide nano-rod.
As shown in Figure 5, the diameter of the manganese dioxide nano-rod that obtains is 20～25nm, and length is 150～250nm.
Claims (8)
1. the preparation method of a manganese dioxide nano-rod the steps include:
(1) manganese salt and alcohol solution are made into mixing solutions, used manganese salt for solubleness in alcohol is: greater than 0.005g/mL, less than 1g/mL;
(2) in mixing solutions, add oxygenant, obtain dark solution, left standstill 1～30 minute;
(3) under mechanical stirring or sonic oscillation condition, in dark solution, add suitable quantity of water, perhaps dilute acid soln, the gradually uniform black precipitate of precipitate particle;
(4) with the black precipitate centrifugation, and water washs, and is drying to obtain manganese dioxide nano-rod under 120 ℃.
2. the preparation method of manganese dioxide nano-rod according to claim 1 is characterized in that manganese salt is Mn (NO
3)
2, perhaps Mn (CH
3COO)
2, perhaps MnCl
2, perhaps MnSO
4, perhaps MnCH
2(COO)
2, perhaps Mn (CH
3CH
2COO)
2, or be above several mixture.
3. the preparation method of manganese dioxide nano-rod according to claim 1 is characterized in that alcohol is methyl alcohol, perhaps ethanol, perhaps ethylene glycol, perhaps propyl alcohol, perhaps propylene glycol, perhaps glycerol, perhaps butanols, perhaps 1,2-two butanols, perhaps 1,3-two butanols, perhaps above several mixture.
4. the preparation method of manganese dioxide nano-rod according to claim 1 is characterized in that: in the step 1, in the alcohol solution, the volume ratio of alcohol and water is greater than 1: 5, less than 10000: 1, or anhydrous alcohol solution.
5. the preparation method of manganese dioxide nano-rod according to claim 1, it is characterized in that: the oxygenant in the step (2) can be air, or oxygen, or hypochlorous acid, or hypochlorite, or hydrogen peroxide, or peroxy acid, or above several mixture.
6. the preparation method of manganese dioxide nano-rod according to claim 1, it is characterized in that: dilute acid soln is salpeter solution in the step (3), or sulphuric acid soln, or acetic acid solution, or above several mixture, the volumetric molar concentration of dilute acid soln is: greater than 0.0001mol/L, less than 5mol/L.
7. the preparation method of manganese dioxide nano-rod according to claim 1 is characterized in that: in the step 3, the volume that adds entry or acid solution by the pure volume of adding 1-10 doubly.
8. the preparation method of manganese dioxide nano-rod according to claim 1 is characterized in that the drying means in the step (4) is spraying drying, perhaps ultra red ray drying, perhaps microwave drying, perhaps fluidized drying.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104409719A (en) * | 2014-12-02 | 2015-03-11 | 兰州理工大学 | Porous spherical lithium manganate cathode material and preparation method thereof |
| CN105595466A (en) * | 2015-11-13 | 2016-05-25 | 无锡桥阳机械制造有限公司 | Mask for preventing and controlling haze and nitric oxide pollution at same time |
| CN105886781A (en) * | 2016-06-29 | 2016-08-24 | 广西桂柳化工有限责任公司 | Method for recovering manganese dioxide from electrolytic manganese anode mud |
| CN107946587A (en) * | 2017-10-26 | 2018-04-20 | 陕西科技大学 | A kind of anode material of lithium-ion battery MnOxPreparation method |
| CN108017091A (en) * | 2017-11-07 | 2018-05-11 | 深圳市晶特智造科技有限公司 | A kind of rod-like nano α-MnO2And its preparation method and application |
| CN110157377A (en) * | 2019-06-24 | 2019-08-23 | 吕梁学院 | Walnut shell biomass C/MnO2The preparation method of microwave absorbing material |
| CN110451586A (en) * | 2019-07-03 | 2019-11-15 | 中山大学 | A kind of anode material for lithium-ion batteries and preparation method thereof with one-dimentional structure |
| CN114105204A (en) * | 2021-11-12 | 2022-03-01 | 中博龙辉装备集团股份有限公司 | Rod-shaped manganese oxide and preparation method and application thereof |
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| CN1673097A (en) * | 2005-03-11 | 2005-09-28 | 华南师范大学 | Prepn process of amorphous manganese dioxide |
| CN101798118A (en) * | 2010-03-11 | 2010-08-11 | 湘潭大学 | Preparation method of manganese dioxide one-dimensional nanomaterial |
| CN101870497A (en) * | 2009-04-24 | 2010-10-27 | 南京理工大学 | Preparation method of microstructure controllable nano-manganese dioxide |
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2012
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Patent Citations (3)
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| CN1673097A (en) * | 2005-03-11 | 2005-09-28 | 华南师范大学 | Prepn process of amorphous manganese dioxide |
| CN101870497A (en) * | 2009-04-24 | 2010-10-27 | 南京理工大学 | Preparation method of microstructure controllable nano-manganese dioxide |
| CN101798118A (en) * | 2010-03-11 | 2010-08-11 | 湘潭大学 | Preparation method of manganese dioxide one-dimensional nanomaterial |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104409719A (en) * | 2014-12-02 | 2015-03-11 | 兰州理工大学 | Porous spherical lithium manganate cathode material and preparation method thereof |
| CN105595466A (en) * | 2015-11-13 | 2016-05-25 | 无锡桥阳机械制造有限公司 | Mask for preventing and controlling haze and nitric oxide pollution at same time |
| CN105886781A (en) * | 2016-06-29 | 2016-08-24 | 广西桂柳化工有限责任公司 | Method for recovering manganese dioxide from electrolytic manganese anode mud |
| CN105886781B (en) * | 2016-06-29 | 2018-01-02 | 广西桂柳化工有限责任公司 | Method for recovering manganese dioxide from electrolytic manganese anode mud |
| CN107946587A (en) * | 2017-10-26 | 2018-04-20 | 陕西科技大学 | A kind of anode material of lithium-ion battery MnOxPreparation method |
| CN107946587B (en) * | 2017-10-26 | 2020-05-12 | 陕西科技大学 | Sodium ion battery negative electrode material MnOxPreparation method of (1) |
| CN108017091A (en) * | 2017-11-07 | 2018-05-11 | 深圳市晶特智造科技有限公司 | A kind of rod-like nano α-MnO2And its preparation method and application |
| CN110157377A (en) * | 2019-06-24 | 2019-08-23 | 吕梁学院 | Walnut shell biomass C/MnO2The preparation method of microwave absorbing material |
| CN110157377B (en) * | 2019-06-24 | 2022-03-25 | 吕梁学院 | Walnut shell biomass C/MnO2Preparation method of microwave absorbing material |
| CN110451586A (en) * | 2019-07-03 | 2019-11-15 | 中山大学 | A kind of anode material for lithium-ion batteries and preparation method thereof with one-dimentional structure |
| CN110451586B (en) * | 2019-07-03 | 2022-04-12 | 中山大学 | Lithium ion battery anode material with one-dimensional structure and preparation method thereof |
| CN114105204A (en) * | 2021-11-12 | 2022-03-01 | 中博龙辉装备集团股份有限公司 | Rod-shaped manganese oxide and preparation method and application thereof |
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Application publication date: 20131030 |