CN100393626C - Method for synthesizing nano-structure of bunchy manganese dioxide - Google Patents
Method for synthesizing nano-structure of bunchy manganese dioxide Download PDFInfo
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- CN100393626C CN100393626C CNB2005100450466A CN200510045046A CN100393626C CN 100393626 C CN100393626 C CN 100393626C CN B2005100450466 A CNB2005100450466 A CN B2005100450466A CN 200510045046 A CN200510045046 A CN 200510045046A CN 100393626 C CN100393626 C CN 100393626C
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Abstract
The present invention provides a method for synthesizing the nanometer structure of bunchy manganese dioxide, which comprises the following procedures: a. in a potassic permanganate solution with the concentration of 0.2 to 1.0 mol/l, a reducing agent and a surface active agent are added to form a transparent solution, the weight ratio of the potassic permanganate solution, the reducing agent and the surface active agent which are stirred is 1: (1 to 2): (1 to 2); b. a strong alkaline solution with the volume of 5 to 10 ml and the concentration of 1 to 4 mol/l is slowly added into the transparent solution in the procedure a, and the two solutions are stirred for 15 to 30 minutes in the room temperature and uniformly mixed; c. the mixed solution is arranged in a hermetic reaction container to completely react under the heating condition and then cooled to reach the room temperature; d. the mixed solution is dried in the temperature of 60 to 90DEG C after washed to obtain the bunchy manganese dioxide nanometer material.
Description
Technical field
The invention belongs to technical field of inorganic chemical industry, relate to preparation of nanomaterials, relate in particular to a kind of synthetic method of manganese dioxide one-dimensional nanostructure of bunchy.
Background technology
In recent years, owing to having a wide range of applications in all many-sides such as nanocomposite optical device, nano electron device and biosensors, nanostructures such as monodimension nanometer material such as nanometer rod, nano wire, nano belt and nanotube receive much attention.(A.P.Alivisatos, Science 1996,271,933) nearest studies show that becomes complicated more one dimension Nano structure as monodimension nanometer material matrix assembling how and just becoming current research focus.And scientist has been found that these complicated one dimension Nano structures demonstrate wide application prospect at the aspects such as separation of DNA.(I.Ichinose et al J.Am.Chem.Soc.2005,127,8296; I.Ichinose et al Nano.Lett.2005,1,97; I.Ichinose J.Am.Chem.Soc.2004,126,7162.) yet, how in liquid phase, monodimension nanometer material to be assembled into complicated more one dimension Nano structure and still to be faced with challenge.
Manganse Dioxide is owing to its distinguished characteristic is widely used in fields such as catalyzer, electrode materials and soft magnetic materials.(Science 1998,279 for A.M.Morales, C.M.Lieber, 208.) in recent years, the preparation of one dimension nano material of manganese dioxide such as nano wire, nano belt, nanometer rod, nanotube has a large amount of reports.And shown electrochemical properties preferably.But the preparation of the manganese dioxide nano line of fasciculation does not appear in the newspapers so far as yet.We adopt a kind of new redox path of preparing to go out the manganese dioxide nano line of bunchy, and products obtained therefrom is the pattern homogeneous not only, and no agglomeration, and output height have shown stronger magnetism characteristic under cold condition.Its synthesis technique is simple, and is with low cost, and productive rate helps suitability for industrialized production up to more than 90%.
Summary of the invention
The purpose of this invention is to provide a kind of simple for process, cost is low, helps the synthetic method of manganese dioxide nano structure of the bunchy of large-scale industrial production.
Purpose of the present invention can realize by following technical measures:
This method is carried out according to the following steps:
A, in 0.2～1.0mol/L potassium permanganate solution, according to potassium permanganate solution: reductive agent: tensio-active agent=1: 1～2: 1～2 weight parts add reductive agent and tensio-active agent down in stirring, and form clear solution; B, the strong base solution of 1～4mol/L of 5～10mL is slowly joined in the clear solution of a operation, stirred mixing under the room temperature 15～30 minutes; C, above-mentioned mixing solutions is inserted in the closed reaction vessel, under heating condition, react completely, then cool to room temperature again; D, after washing in 60～90 ℃ down dry, the nano material of manganese dioxide of bunchy.
Purpose of the present invention also can realize by following technical measures:
Described reductive agent is a short carbon chain alcohol; Described short carbon chain alcohol is selected from n-Heptyl alcohol, glycerol, isooctyl alcohol or propyl carbinol; Described tensio-active agent is that concentration is the soluble surfactant of 5～30 (weight) %; Described soluble surfactant is selected from cetyl trimethylammonium bromide, sodium cetanesulfonate, poly(oxyethylene glycol) 400 or Polyethylene Glycol-600; Described highly basic is that concentration is the alkali-metal oxyhydroxide of 1～4mol/L; Described alkali-metal oxyhydroxide is selected from sodium hydroxide, potassium hydroxide or lithium hydroxide; Described reaction Heating temperature is 100～220 ℃, and the described reaction times is 12～48 hours; It is the acid solution of 0.1～0.2 (weight) % that deionized water or content are adopted in described washing.
Production technique of the present invention is simple, and cost is low, and equipment requirements is not harsh, helps large-scale production; The present invention not only provides a kind of operational path for preparing the manganese dioxide nano structure of bunchy, has also filled up the blank of the manganese dioxide one-dimensional nanostructure that bunchy is not arranged so far.Adopt X ray powder diffracting technology, transmissions such as TEM, SEM, scanning technique to product characterize.Characterize with the magnetism characteristic of superconduction amount magnetometer product.
Embodiment:
Embodiment 1:
The potassium permanganate that takes by weighing 1 gram 0.2mol/L places beaker, form clear solution with the dissolving of 5ml deionized water and stirring, pour the Polyethylene Glycol-600 that 5ml propyl carbinol and 5ml concentration are 5 (weight) % then into, stirred 10 minutes, the 2mol/L potassium hydroxide solution 7ml that will prepare in advance then dropwise adds in the above-mentioned mixing solutions, stir after 20 minutes, be moved in the closed reactor, reacted 24 hours down at 120 ℃, with the closed reactor cool to room temperature, again with behind the deionized water wash in 60 ℃ of dry products.Product is accredited as α-MnO through X-ray powder diffraction
2TEM and SEM Electronic Speculum testing product are the manganese dioxide one-dimensional nanostructure of the bunchy of high yield.
Embodiment 2:
The potassium permanganate that takes by weighing 1 gram 0.2mol/L places beaker, form clear solution with the dissolving of 5ml deionized water and stirring, pour the Polyethylene Glycol-600 that 5ml propyl carbinol and 8ml concentration are 30 (weight) % then into, stirred 10 minutes, the 2mol/L potassium hydroxide solution 6ml that will prepare in advance then dropwise adds in the above-mentioned mixing solutions, stir after 15 minutes, be moved in the closed reactor, reacted 24 hours down at 100 ℃, with the closed reactor cool to room temperature, again with behind the deionized water wash in 90 ℃ of dry products.Product is accredited as α-MnO through X-ray powder diffraction
2TEM and SEM Electronic Speculum testing product are the manganese dioxide one-dimensional nanostructure of the bunchy of high yield.
Embodiment 3:
The potassium permanganate that takes by weighing 1 gram 0.2mol/L places beaker, form clear solution with the dissolving of 5ml deionized water and stirring, pour the Polyethylene Glycol-600 that 5ml propyl carbinol and 10ml concentration are 15 (weight) % then into, stirred 10 minutes, the 2mol/L potassium hydroxide solution 9ml that will prepare in advance then dropwise adds in the above-mentioned mixing solutions, stir after 30 minutes, be moved in the closed reactor, reacted 24 hours down at 200 ℃, with the closed reactor cool to room temperature, again with behind the deionized water wash in 80 ℃ of dry products.Product is accredited as α-MnO through X-ray powder diffraction
2TEM and SEM Electronic Speculum testing product are the manganese dioxide one-dimensional nanostructure of the bunchy of high yield.
Embodiment 4:
The potassium permanganate that takes by weighing 1 gram 1.0mol/L places beaker, form clear solution with the dissolving of 5ml deionized water and stirring, add the cetyl trimethylammonium bromide that 10ml isooctyl alcohol and 5ml concentration are 8 (weight) % then, stirred 10 minutes, the 2mol/L sodium hydroxide solution 5ml that will prepare in advance then dropwise adds in the above-mentioned mixing solutions, stir after 30 minutes, be moved in the closed reactor, reacted 24 hours down at 180 ℃, with the closed reactor cool to room temperature, again with behind the deionized water wash in 70 ℃ of dry products.Product is accredited as α-MnO through X-ray powder diffraction
2TEM and SEM Electronic Speculum testing product are the manganese dioxide one-dimensional nanostructure of the bunchy of high yield.
Embodiment 5:
The potassium permanganate that takes by weighing 1 gram 1.0mol/L places beaker, form clear solution with the dissolving of 5ml deionized water and stirring, add the cetyl trimethylammonium bromide that 10ml isooctyl alcohol and 10ml concentration are 18 (weight) % then, stirred 10 minutes, the 2mol/L sodium hydroxide solution 10ml that will prepare in advance then dropwise adds in the above-mentioned mixing solutions, stir after 25 minutes, be moved in the closed reactor, reacted 24 hours down at 200 ℃, with the closed reactor cool to room temperature, be that the acid solution washing back of 0.2 (weight) % is in 80 ℃ of dry products with content again.Product is accredited as α-MnO through X-ray powder diffraction
2TEM and SEM Electronic Speculum testing product are the manganese dioxide one-dimensional nanostructure of the bunchy of high yield.
Embodiment 6:
The potassium permanganate that takes by weighing 1 gram 1.0mol/L places beaker, form clear solution with the dissolving of 5ml deionized water and stirring, add the cetyl trimethylammonium bromide that 10ml isooctyl alcohol and 7ml concentration are 30 (weight) % then, stirred 10 minutes, the 2mol/L sodium hydroxide solution 8ml that will prepare in advance then dropwise adds in the above-mentioned mixing solutions, stir after 15 minutes, be moved in the closed reactor, reacted 12 hours down at 100 ℃, with the closed reactor cool to room temperature, again with behind the deionized water wash in 60 ℃ of dry products.Product is accredited as α-MnO through X-ray powder diffraction
2TEM and SEM Electronic Speculum testing product are the manganese dioxide one-dimensional nanostructure of the bunchy of high yield.
Embodiment 7:
The potassium permanganate that takes by weighing 1 gram 0.5mol/L places beaker, form clear solution with the dissolving of 5ml deionized water and stirring, add the poly(oxyethylene glycol) 400 that 5ml glycerol and 5ml concentration are 20 (weight) % then, stirred 10 minutes, the 3mol/L lithium hydroxide solution 5ml that will prepare in advance then dropwise adds in the above-mentioned mixing solutions, stir after 20 minutes, be moved in the closed reactor, reacted 48 hours down at 110 ℃, with the closed reactor cool to room temperature, again with behind the deionized water wash in 90 ℃ of dry products.Product is accredited as α-MnO through X-ray powder diffraction
2TEM and SEM Electronic Speculum testing product are the manganese dioxide one-dimensional nanostructure of the bunchy of high yield.
Embodiment 8:
The potassium permanganate that takes by weighing 1 gram 0.5mol/L places beaker, form clear solution with the dissolving of 5ml deionized water and stirring, add the poly(oxyethylene glycol) 400 that 5ml glycerol and 10ml concentration are 5 (weight) % then, stirred 10 minutes, the 3mol/L lithium hydroxide solution 7ml that will prepare in advance then dropwise adds in the above-mentioned mixing solutions, stir after 15 minutes, be moved in the closed reactor, reacted 45 hours down at 170 ℃, with the closed reactor cool to room temperature, be that the acid solution washing back of 0.2 (weight) % is in 70 ℃ of dry products with content again.Product is accredited as α-MnO through X-ray powder diffraction
2TEM and SEM Electronic Speculum testing product are the manganese dioxide one-dimensional nanostructure of the bunchy of high yield.
Embodiment 9:
The potassium permanganate that takes by weighing 1 gram 0.5mol/L places beaker, form clear solution with the dissolving of 5ml deionized water and stirring, add the poly(oxyethylene glycol) 400 that 5ml glycerol and 7ml concentration are 30 (weight) % then, stirred 10 minutes, the 3mol/L lithium hydroxide solution 10ml that will prepare in advance then dropwise adds in the above-mentioned mixing solutions, stir after 30 minutes, be moved in the closed reactor, reacted 25 hours down at 200 ℃, with the closed reactor cool to room temperature, again with behind the deionized water wash in 60 ℃ of dry products.Product is accredited as α-MnO through X-ray powder diffraction
2TEM and SEM Electronic Speculum testing product are the manganese dioxide one-dimensional nanostructure of the bunchy of high yield.
The potassium permanganate that takes by weighing 1 gram 0.8mol/L places beaker, form clear solution with the dissolving of 5ml deionized water and stirring, add the sodium cetanesulfonate that 10ml n-Heptyl alcohol and 10ml concentration are 30 (weight) % then, stirred 10 minutes, the 3mol/L lithium hydroxide solution 8ml that will prepare in advance then dropwise adds in the above-mentioned mixing solutions, stir after 25 minutes, be moved in the closed reactor, reacted 12 hours down at 160 ℃, with the closed reactor cool to room temperature, be that the acid solution washing back of 0.2 (weight) % is in 80 ℃ of dry products with content again.Product is accredited as α-MnO through X-ray powder diffraction
2TEM and SEM Electronic Speculum testing product are the manganese dioxide one-dimensional nanostructure of the bunchy of high yield.
Embodiment 11
The potassium permanganate that takes by weighing 1 gram 0.8mol/L places beaker, form clear solution with the dissolving of 5ml deionized water and stirring, add the sodium cetanesulfonate that 10ml n-Heptyl alcohol and 8ml concentration are 5 (weight) % then, stirred 10 minutes, the 3mol/L sodium hydroxide solution 10ml that will prepare in advance then dropwise adds in the above-mentioned mixing solutions, stir after 25 minutes, be moved in the closed reactor, reacted 30 hours down at 120 ℃, with the closed reactor cool to room temperature, again with behind the deionized water wash in 75 ℃ of dry products.Product is accredited as α-MnO through X-ray powder diffraction
2TEM and SEM Electronic Speculum testing product are the manganese dioxide one-dimensional nanostructure of the bunchy of high yield.
Embodiment 12
The potassium permanganate that takes by weighing 1 gram 0.8mol/L places beaker, form clear solution with the dissolving of 5ml deionized water and stirring, add the sodium cetanesulfonate that 10ml n-Heptyl alcohol and 5ml concentration are 5 (weight) % then, stirred 10 minutes, the 3mol/L potassium hydroxide solution 5ml that will prepare in advance then dropwise adds in the above-mentioned mixing solutions, stir after 15 minutes, be moved in the closed reactor, reacted 20 hours down at 190 ℃, with the closed reactor cool to room temperature, with behind the deionized water wash in 80 ℃ of dry products.Product is accredited as α-MnO through X-ray powder diffraction
2TEM and SEM Electronic Speculum testing product are the manganese dioxide one-dimensional nanostructure of the bunchy of high yield.
Description of drawings
Fig. 1 is the manganese dioxide one-dimensional nanostructure X-ray powder diffraction figure of the bunchy of the embodiment of the invention 1 preparation;
Fig. 2 is the manganese dioxide one-dimensional nanostructure low power scanned photograph (SEM) of the bunchy of the embodiment of the invention 1 preparation;
Fig. 3 is the manganese dioxide one-dimensional nanostructure high power scanned photograph (SEM) of the bunchy of the embodiment of the invention 1 preparation;
Fig. 4 is the manganese dioxide one-dimensional nanostructure transmission electron microscope photo (TEM) of the bunchy of the embodiment of the invention 1 preparation;
Fig. 5 is the temperature-susceptibility curve (M-T curve) of manganese dioxide one-dimensional nanostructure of the bunchy of the embodiment of the invention 1 preparation;
Fig. 6 is the externally-applied magnetic field-susceptibility curve (M-H curve) of manganese dioxide one-dimensional nanostructure of the bunchy of the embodiment of the invention 1 preparation.
Claims (7)
1. the synthetic method of the manganese dioxide nano structure of bunchy is characterized in that this method carries out according to the following steps:
A, in 0.2～1.0mol/L potassium permanganate solution, according to potassium permanganate solution: reductive agent: tensio-active agent=1: 1～2: 1～2 weight parts add reductive agent and tensio-active agent down in stirring, and form clear solution;
B, the strong base solution of 1～4mol/L of 5～10mL is slowly joined in the clear solution, stirred mixing under the room temperature 15～30 minutes;
C, the solution of mixing is inserted in the closed reaction vessel, under heating condition, react completely, then cool to room temperature again;
D, after washing in 60～90 ℃ down dry, the nano material of manganese dioxide of bunchy;
Described reductive agent is a short carbon chain alcohol; Described tensio-active agent is that weight concentration is 5～30% soluble surfactant.
2. the synthetic method of the manganese dioxide nano structure of bunchy according to claim 1 is characterized in that described short carbon chain alcohol is selected from n-Heptyl alcohol, glycerol, isooctyl alcohol or propyl carbinol.
3. the synthetic method of the manganese dioxide nano structure of bunchy according to claim 1 is characterized in that described soluble surfactant is selected from cetyl trimethylammonium bromide, sodium cetanesulfonate, poly(oxyethylene glycol) 400 or Polyethylene Glycol-600.
4. the synthetic method of the manganese dioxide nano structure of bunchy according to claim 1 is characterized in that described highly basic is that concentration is the alkali-metal oxyhydroxide of 1～4mol/L.
5. the synthetic method of the manganese dioxide nano structure of bunchy according to claim 6 is characterized in that described alkali-metal oxyhydroxide is selected from sodium hydroxide, potassium hydroxide or lithium hydroxide.
6. the synthetic method of the manganese dioxide nano structure of bunchy according to claim 1 is characterized in that described reaction Heating temperature is 100～220 ℃, and the described reaction times is 12～48 hours.
7. the synthetic method of the manganese dioxide nano structure of bunchy according to claim 1 is characterized in that described washing employing deionized water or weight concentration are 0.1～0.2% acid solution.
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| CN102689929A (en) * | 2012-06-12 | 2012-09-26 | 东华大学 | Method for preparing ultralong MnO2 nanowire supercapacitor material |
| CN103480267B (en) * | 2013-04-22 | 2016-03-30 | 清华大学 | Material for air purification and its preparation method and application |
| CN105329947A (en) * | 2015-10-28 | 2016-02-17 | 上海大学 | Preparation method of nano-manganese oxide of flocculent structure |
| CN105502504A (en) * | 2016-02-17 | 2016-04-20 | 上海应用技术学院 | Preparation method of manganese dioxide nanowire |
| CN106745285B (en) * | 2017-03-01 | 2018-07-03 | 哈尔滨工业大学 | A kind of α-MnO2The preparation method of nano wire |
| CN112266023A (en) * | 2020-11-17 | 2021-01-26 | 河南大学 | Manganese dioxide nanostructure with controllable morphology, preparation method and application thereof |
| CN113193178A (en) * | 2020-12-07 | 2021-07-30 | 北京服装学院 | Preparation method of manganese dioxide nanosheet coated carbon fiber for supplying power to intelligent clothes |
| CN113694918A (en) * | 2021-08-27 | 2021-11-26 | 珠海格力电器股份有限公司 | Manganese oxide catalyst catalyzed by formaldehyde and preparation method thereof |
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| 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 |
| CN1438181A (en) * | 2002-12-24 | 2003-08-27 | 上海大学 | Method for preparing nano manganese dioxide |
| CN1513767A (en) * | 2002-12-31 | 2004-07-21 | 章浩龙 | Preparation method of superfine manganese dioxide |
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| 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 |
| CN1438181A (en) * | 2002-12-24 | 2003-08-27 | 上海大学 | Method for preparing nano manganese dioxide |
| CN1513767A (en) * | 2002-12-31 | 2004-07-21 | 章浩龙 | Preparation method of superfine manganese dioxide |
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