CN102502848A - Solvothermal preparation method for alkali manganese oxide nanowires - Google Patents
Solvothermal preparation method for alkali manganese oxide nanowires Download PDFInfo
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- CN102502848A CN102502848A CN2011103300540A CN201110330054A CN102502848A CN 102502848 A CN102502848 A CN 102502848A CN 2011103300540 A CN2011103300540 A CN 2011103300540A CN 201110330054 A CN201110330054 A CN 201110330054A CN 102502848 A CN102502848 A CN 102502848A
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Abstract
The invention discloses a solvothermal preparation method for alkali manganese oxide nanowires. Manganese sulfate aqueous solution with the concentration of 0.5 to 2.0 mol/L and potassium permanganate aqueous solution with the concentration of 0.5 to 2.0 mol/L are mixed, wherein molar ratio of manganese sulfate and potassium permanganate ranges from 1/3 to 4, n-butyl alcohol aqueous solution with the volume ratio of 1/2 to 2 is added, the solution is evenly mixed, at the temperature of 120 to 220 DEG C, the solution is subjected to solvothermal reaction for 6 to 24 hours, and then alkali manganese oxide nanowires are obtained. The solvothermal preparation method for alkali manganese oxide nanowires is simple in process operation and environment-friendly. Products can be obtained directly in the solution at a low temperature without roasting. The obtained alkali manganese oxide is high in purity, narrow in size distribution and good in dispersity, and the alkali manganese oxide nanowires are suitable for industrial production. The solvothermal preparation method for alkali manganese oxide nanowires is capable of preparing high-purity and fine alkali manganese oxide nanowires suitable for industrial production without surface active agents and templates.
Description
Technical field
The invention belongs to the inorganic nano material preparing technical field, be specifically related to the method that a kind of solvent thermal prepares alkali formula manganese oxide nano wire.
Background technology
Alkali formula manganese oxide (III), i.e. MnO (OH), read like hydroxide oxygen manganese is generally in the zinc-manganse dioxide dry cell Manganse Dioxide and inhales and obtain electronics behind the hydrogen and be reduced the electrode reaction resultant that forms.Alkali formula manganese oxide is the solid black powder at normal temperatures and pressures, is a kind of very important solid matter, can be made into the important source material that electronic industry is produced the Mn-Zn ferrite soft magnetic materials through oxidation or reduction.It is also having a very wide range of applications aspect ion-exchange material, electrochromic material, electrochemical material and the catalytic material.
In recent years; Discovering of relevant nano-functional material, the microstructure of functional materials such as grain size and distribution, crystal morphology, surperficial key property, crystallinity, particles dispersed property etc. have very big influence to the machining property of light, electricity, catalytic performance and the material of device.Adopting easyly to be prone to industrialized compound method and to prepare that particle is tiny, dispersity is high, size is even, the nano-powder of pattern homogeneous, is the prerequisite for preparing high performance material.In order to satisfy people to the high performance material demand, the novel process of preparation functional materials ultrafine powder continues to bring out.At present; It is multiple that the method for preparing MnO (OH) mainly contains low temperature neutralisation under sol-gel method, template, the low-intensity magnetic field, hydro-thermal-electrochemical process, reverse micelle method, ozone oxidation method etc.; And topmost compound method is a hydrothermal method, as being the MnOOH that reductive agent prepares the racemosus shape with the polyoxyethylene glycol, prepares tetragonal prism MnOOH nanometer rod through adding the cetyl trimethylammonium bromide tensio-active agent; With toluene is that reductive agent prepares the MnOOH nano wire, to sacrifice MnO
2Template prepares MnOOH nanotube etc.But this method need add tensio-active agent or template or some difficult volatilization and virose solvent, and the preparation method is complicated, and environment is unfriendly.
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Summary of the invention
The objective of the invention is to the above-mentioned defective that exists in the prior art, provide that a kind of preparation method is simple, environmental friendliness, product purity is high, particle is tiny and be evenly distributed, pattern is single, the solvent process for thermosynthesizing of the alkali formula manganese oxide nano wire of good dispersivity.
The inventive method comprises the step of following order:
(1) at first, with concentration be 0.5 ~ 2.0 mol/L manganese sulfate solution and concentration be 0.5 ~ 2.0 mol/L potassium permanganate solution mix mixed solution, wherein the molar ratio range of manganous sulfate and potassium permanganate is 1:3 ~ 4:1;
(2) in step (1) gained mixed solution, add n-butanol aqueous solution, the volume ratio of propyl carbinol and water is 1:2 ~ 2:1 in the n-butanol aqueous solution;
(3) step (2) gained mixed solution is stirred to mixes, is solvent thermal reaction 6 ~ 24 h under 120 ~ 220 ℃ of conditions in temperature, alkali formula manganese oxide nano wire;
Wherein, the volumetric molar concentration of said manganous sulfate in mixed solution is 0.1 ~ 0.5 mol/L, and the volumetric molar concentration of potassium permanganate in mixed solution is 0.3 ~ 1.0 mol/L.
Further, the volume ratio of propyl carbinol and water is preferably 1:2 ~ 1:1 in the said n-butanol aqueous solution of step (2).
The temperature of the said solvent thermal reaction of step (3) is preferably 160 ~ 200 ℃.
Said solvent thermal reaction is in having the teflon-lined autoclave, to carry out.
The present invention adopts solvent-thermal method; Through adding organic solvent; Obtain the product purity height, particle is tiny and be evenly distributed, pattern is single, the alkali formula manganese oxide of good dispersivity; And need not to add any tensio-active agent or template effect, under simple and easy to do operational condition, obtained alkali formula manganese oxide nano wire.Gained alkali formula manganese oxide nanowire size is even, and line length reaches several microns, and diameter is about 50 nm, and its particle size can be controlled through reaction conditions.The present invention has green economy, environmental friendliness, low temperature, need not calcine advantages such as can in solution, directly obtaining product, and is applicable to suitability for industrialized production.
Description of drawings
Fig. 1 is the XRD figure of the prepared alkali formula manganese oxide nano wire of the embodiment of the invention 1 to embodiment 5.
Fig. 2 is the stereoscan photograph (JEOL 2010 type high-resolution-ration transmission electric-lens scanners, 200 kV) of the prepared alkali formula manganese oxide nano wire of the embodiment of the invention 3.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is described in further detail.
Embodiment 1:
2 ml, 0.5 mol/L manganese sulfate solution and 4 ml, 0.5 mol/L potassium permanganate solution are mixed, and joining 4 ml volume ratios is in the n-butanol aqueous solution of 1:1, and making manganous sulfate is 1:2 with potassium permanganate molar ratio in the solution after mixing, and stirs.Mixed solution is transferred to has in the teflon-lined autoclave, is solvent thermal reaction 6 h under 140 ℃ of conditions in temperature, get final product alkali formula manganese oxide nano wire.Shown in curve among Fig. 11, all diffraction peaks of product can both be corresponding with the base peak (JCPDS No. 41-1379) of the MnO (OH) of bottom.According to Scherrer formula
, can estimate that the dimension D on 022 orientation is 46 nm.
Embodiment 2:
2 ml, 1.0 mol/L manganese sulfate solutions and 4 ml, 1.0 mol/L potassium permanganate solutions are mixed, and joining 4 ml volume ratios is in the n-butanol aqueous solution of 1:1, and making manganous sulfate is 1:2 with potassium permanganate molar ratio in the solution after mixing, and stirs.Mixed solution is transferred to has in the teflon-lined autoclave, is solvent thermal reaction 6 h under 220 ℃ of conditions in temperature, get final product alkali formula manganese oxide nano wire.Shown in curve among Fig. 12, all diffraction peaks of product can both be corresponding with the base peak (JCPDS No. 41-1379) of the MnO (OH) of bottom.According to Scherrer formula
, can estimate that the dimension D on 022 orientation is about 54 nm.
Embodiment 3:
4 ml, 1.0 mol/L manganese sulfate solutions and 2 ml, 1.0 mol/L potassium permanganate solutions are mixed, and joining 4 ml volume ratios is in the n-butanol aqueous solution of 1:1, and making manganous sulfate is 2:1 with potassium permanganate molar ratio in the solution after mixing, and stirs.Mixed solution is transferred to has in the teflon-lined autoclave, is solvent thermal reaction 24 h under 160 ℃ of conditions in temperature, get final product alkali formula manganese oxide nano wire.Shown in curve among Fig. 13, all diffraction peaks of product can both be corresponding with the base peak (JCPDS No. 41-1379) of the MnO (OH) of bottom.According to Scherrer formula
, can estimate that the dimension D on 022 orientation is about 48 nm.Adopt JEOL 2010 type high-resolution-ration transmission electric-lens scanners (acceleration voltage is 200 kV) that sample has been carried out morphology observation, as shown in Figure 2.As can be seen from Figure 2, the gained sample is the nano wire of pattern homogeneous, and linear diameter is about 45-60 nm, and line length reaches to several microns.
The electromicroscopic photograph of the embodiment of the invention 1 to embodiment 5 products therefrom is basic the same with Fig. 2, no longer provides one by one at each embodiment.
Embodiment 4:
4 ml, 1.0 mol/L manganese sulfate solutions and 2 ml, 1.0 mol/L potassium permanganate solutions are mixed, and joining 4 ml volume ratios is in the n-butanol aqueous solution of 1:2, and making manganous sulfate is 2:1 with potassium permanganate molar ratio in the solution after mixing, and stirs.Mixed solution is transferred to has in the teflon-lined autoclave, is solvent thermal reaction 12 h under 180 ℃ of conditions in temperature, get final product alkali formula manganese oxide nano wire.Shown in curve among Fig. 14, all diffraction peaks of product can both be corresponding with the base peak (JCPDS No. 41-1379) of the MnO (OH) of bottom.According to Scherrer formula
, can estimate that the dimension D on 022 orientation is about 50 nm.
Embodiment 5:
2 ml, 2.0 mol/L manganese sulfate solutions and 1 ml, 1.0 mol/L potassium permanganate solutions are mixed, and joining 7 ml volume ratios is in the n-butanol aqueous solution of 1:2, and making manganous sulfate is 4:1 with potassium permanganate molar ratio in the solution after mixing, and stirs.Mixed solution is transferred to has in the teflon-lined autoclave, is solvent thermal reaction 12 h under 200 ℃ of conditions in temperature, get final product alkali formula manganese oxide nano wire.Shown in curve among Fig. 15, all diffraction peaks of product can both be corresponding with the base peak (JCPDS No. 41-1379) of the MnO (OH) of bottom.According to Scherrer formula
, can estimate that the dimension D on 022 orientation is about 52 nm.
Can be known that by the foregoing description the present invention adopts solvent-thermal method synthetic alkali formula manganese oxide nano wire, and prior art need add tensio-active agent or template or some difficult volatilization and virose solvent, the preparation method is complicated, and environment is unfriendly.Compare with existing compound method, the present invention has green economy, environmental friendliness, low temperature, need not calcine, can in solution, directly obtain advantages such as product.And the alkali formula manganese oxide nano wire that the adding through the special organic solvent of n-butanol aqueous solution of the present invention makes the present invention make is more even, is about several microns, and mean diameter is about 50 nm, and be not easy to reunite, good dispersivity.And the alkali formula manganese oxide of high degree of dispersion, high-ratio surface can be strengthened performances such as its electrochemical properties, magnetic, air-sensitive, catalysis, thereby also can strengthen its application in engineering fields such as magneticsubstance, transmitter, catalyzer.
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Claims (4)
1. a solvent thermal prepares the method for alkali formula manganese oxide nano wire, it is characterized in that comprising the step of following order:
(1) at first, with concentration be 0.5～2.0 mol/L manganese sulfate solution and concentration be 0.5～2.0 mol/L potassium permanganate solution mix mixed solution, wherein the molar ratio range of manganous sulfate and potassium permanganate is 1:3～4:1;
(2) in step (1) gained mixed solution, add n-butanol aqueous solution, the volume ratio of propyl carbinol and water is 1:2～2:1 in the n-butanol aqueous solution;
(3) step (2) gained mixed solution is stirred to mixes, is solvent thermal reaction 6～24 h under 120～220 ℃ of conditions in temperature, alkali formula manganese oxide nano wire;
Wherein, the volumetric molar concentration of said manganous sulfate in mixed solution is 0.1～0.5 mol/L, and the volumetric molar concentration of potassium permanganate in mixed solution is 0.3～1.0 mol/L.
2. solvent thermal according to claim 1 prepares the method for alkali formula manganese oxide nano wire, it is characterized in that: the volume ratio of propyl carbinol and water is preferably 1:2～1:1 in the said n-butanol aqueous solution of step (2).
3. solvent thermal according to claim 1 prepares the method for alkali formula manganese oxide nano wire, it is characterized in that: the temperature of the said solvent thermal reaction of step (3) is preferably 160～200 ℃.
4. solvent thermal according to claim 1 prepares the method for alkali formula manganese oxide nano wire, it is characterized in that: said solvent thermal reaction is in having the teflon-lined autoclave, to carry out.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103399040A (en) * | 2013-07-17 | 2013-11-20 | 武汉工程大学 | Gas-sensitive material for detecting acetaldehyde and method for producing gas-sensitive component by utilizing gas-sensitive material |
| CN104211123A (en) * | 2014-09-16 | 2014-12-17 | 吉林大学 | Preparation method for manganese oxide nano rods |
| CN108059191A (en) * | 2018-01-24 | 2018-05-22 | 安徽大学 | Basic manganese oxide with nanowire morphology and preparation method thereof |
| CN110794633A (en) * | 2019-12-02 | 2020-02-14 | 上海第二工业大学 | Manganese dioxide nanowire-based electrochromic device and preparation method thereof |
| CN111020881A (en) * | 2019-12-09 | 2020-04-17 | 南京工业大学 | Preparation method of multifunctional synergistic hierarchical pore air purification membrane |
| CN111533171A (en) * | 2020-04-07 | 2020-08-14 | 华侨大学 | Simple calcination method for preparing porous MnO2Method (2) |
| CN114682252A (en) * | 2022-04-22 | 2022-07-01 | 北京清新环境技术股份有限公司 | Manganese catalyst, preparation method and application thereof |
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| WO2007020218A1 (en) * | 2005-08-12 | 2007-02-22 | Akzo Nobel N.V. | Process to remove non-biodegradable compounds from an aqueous composition and apparatus therefor |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103399040A (en) * | 2013-07-17 | 2013-11-20 | 武汉工程大学 | Gas-sensitive material for detecting acetaldehyde and method for producing gas-sensitive component by utilizing gas-sensitive material |
| 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 |
| CN104211123A (en) * | 2014-09-16 | 2014-12-17 | 吉林大学 | Preparation method for manganese oxide nano rods |
| CN108059191A (en) * | 2018-01-24 | 2018-05-22 | 安徽大学 | Basic manganese oxide with nanowire morphology and preparation method thereof |
| CN110794633A (en) * | 2019-12-02 | 2020-02-14 | 上海第二工业大学 | Manganese dioxide nanowire-based electrochromic device and preparation method thereof |
| CN110794633B (en) * | 2019-12-02 | 2022-07-12 | 上海第二工业大学 | Manganese dioxide nanowire-based electrochromic device and preparation method thereof |
| CN111020881A (en) * | 2019-12-09 | 2020-04-17 | 南京工业大学 | Preparation method of multifunctional synergistic hierarchical pore air purification membrane |
| CN111533171A (en) * | 2020-04-07 | 2020-08-14 | 华侨大学 | Simple calcination method for preparing porous MnO2Method (2) |
| CN111533171B (en) * | 2020-04-07 | 2022-07-22 | 华侨大学 | Simple calcination method for preparing porous MnO2Method (2) |
| CN114682252A (en) * | 2022-04-22 | 2022-07-01 | 北京清新环境技术股份有限公司 | Manganese catalyst, preparation method and application thereof |
| CN114682252B (en) * | 2022-04-22 | 2024-01-05 | 北京清新环境技术股份有限公司 | Manganese catalyst and preparation method and application thereof |
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Application publication date: 20120620 |