CN103193273A - Preparation method of extra-long manganese dioxide nanowires - Google Patents
Preparation method of extra-long manganese dioxide nanowires Download PDFInfo
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Abstract
The invention discloses a preparation method of extra-long manganese dioxide nanowires. The method comprises using manganese sulfate as a reducing agent, potassium chlorate as an oxidizing agent, and potassium acetate and acetic acid as an additive, performing a hydrothermal reaction for 6-24 hours under 140-200 DEG C in a polytetrafluoroethylene-lined autoclave, naturally cooling, washing and filtering products, and drying to obtain the extra-long manganese dioxide nanowires with a diameter of 50-150 nanometers and a length of more than 100 [mu]m. The method can synthesize the extra-long manganese dioxide nanowires for one step, is relatively low in synthesis temperature and production cost, accords with conditions of large-scale industrial application, and has a wide application prospect.
Description
Technical field
The invention belongs to technical field of inorganic nanometer material, relate to a kind of preparation method of overlength manganese dioxide nano line.
Background technology
Manganse Dioxide is a kind of oxide compound with essential industry purposes, it has ion-exchange and molecular adsorption performance, can be used as ion(ic)sieve, molecular sieve and catalyzer, it has superior electrochemistry and magnetic performance again simultaneously, can be used as positive electrode material and the novel magnetic material of lithium ion battery.The special character of nano material is conducive to the conduction of electronics such as one dimension manganese dioxide nano line simultaneously.Manganese dioxide nano line as existing document Britain " chemical communication " (Chemical Communications, 2011 4 phases 1264 pages) report one dimension can be used for ultracapacitor.And there is the document U.S. " nanometer wall bulletin " (Nano Letters, 2010 10 phases 3852 pages) the report manganese dioxide nano line also can be for the preparation of the lithium manganate nano-material.
The preparation method of preparation manganese dioxide nano line is many at present, mainly contains sol-gel method, hydrothermal method, the precipitator method, electrical spinning method, vapour deposition process etc.It is good that vapour deposition process can make crystalline structure, purity height, the nano wire of even size distribution Manganse Dioxide, and good reproducibility; But vapour deposition process generally needs pyroreaction, and this has just determined that also it is higher to equipment requirements, invests greatlyyer, and operational condition is harshness etc. relatively.The liquid phase method reaction conditions is realization easily comparatively speaking, and can add the growth that a lot of additives are regulated and control the manganese dioxide nano line, and therefore the liquid phase methods that adopt prepare the manganese dioxide nano line more now.But except hydrothermal method, general liquid phase method all needs through high-temperature calcination, and this not only consumes a large amount of energy, and products therefrom is reunited easily, cause distribution of sizes inhomogeneous, prepare the just further calcining of needs of manganese dioxide nano line as Chinese patent 201010614448.4 used sol-gel methodes.Hydro-thermal reaction is to carry out under non-confined condition, compares with other wet chemistry methods to have the reaction conditions close friend, and low temperature does not need calcining can directly obtain product in solution, and the product purity height, advantages such as even size distribution.About Hydrothermal Preparation manganese dioxide nano line, existing document Germany " advanced material " (Advanced Materials, 2004 19 phases 1729 pages) is report to some extent.Simultaneously also there is the part Chinese patent that the manganese dioxide nano line is reported, as 02100707.1,200510014876.2,201210193021.0 etc.
But at present method all can't prepare length greater than the manganese dioxide nano line of 100 μ m under mild conditions, and is that the preparation that additive is controlled the Manganse Dioxide overlong nanowire does not have document or patent report as yet with acetic acid and Potassium ethanoate.When growing for growth material in view of acetate ion there is provide protection the side, in this patent, we are additive with acetic acid and Potassium ethanoate, have prepared overlength manganese dioxide nano line under hydrothermal condition.
Summary of the invention
The present invention's purpose is to overcome the shortcoming of prior art, and a kind of preparation method of overlength manganese dioxide nano line is provided.
Being achieved through the following technical solutions of the object of the invention:
A kind of preparation method of overlength manganese dioxide nano line may further comprise the steps:
Be reductive agent manganous sulfate and the equimolar oxygenant chloric acid potassium of 1 ~ 3 mol/L with concentration, concentration is that the Potassium ethanoate of 0.5 ~ 1.5 mol/L and equimolar acetic acid are that additive is added to the water to stir and forms homogeneous solution, then carry out hydro-thermal reaction, after washing and filtering, oven dry, can obtain overlength manganese dioxide nano line again.
The volumetric molar concentration of described reductive agent manganous sulfate and oxygenant chloric acid potassium is 1.5 ~ 2 mol/L.
The volumetric molar concentration of described additive Potassium ethanoate and acetic acid is 0.75 ~ 1 mol/L.
Described hydrothermal temperature is 140 ~ 200 ℃, and the hydro-thermal reaction time is 6 ~ 24 h.
This method is reductive agent with the manganous sulfate, and Potcrate is oxygenant, is additive with Potassium ethanoate and acetic acid, in the teflon-lined autoclave, in 140 ~ 200 ℃ of following hydro-thermal reaction 6 ~ 24 h, can obtain overlength manganese dioxide nano line.
For further realizing the present invention, described hydrothermal temperature is preferably at 160 ~ 180 ℃, and the concentration of described reductive agent and oxygenant is preferably 1.5～2 mol/L, and the concentration of Potassium ethanoate and acetic acid additive is preferably 0.75 ~ 1 mol/L.
The invention has the beneficial effects as follows:
The invention provides a kind of preparation method of overlength manganese dioxide nano line, compare with other wet chemistry methods and have environmental friendliness, low temperature can directly obtain the advantage of product in solution.And product manganese dioxide nano linear dimension length is greater than 100 μ m, and diameter is evenly distributed between 50 ~ 150 nm, and the surface is rich in a large amount of hydroxyls and is conducive to further modification.
Description of drawings
The XRD spectra of the manganese dioxide nano line of Fig. 1 embodiment of the invention 2 preparations.
The sem photograph of the manganese dioxide nano line of Fig. 2 embodiment of the invention 4 preparations.
The transmission electron microscope picture of the manganese dioxide nano line of Fig. 3 embodiment of the invention 7 preparations.
Embodiment:
Embodiment 1:
Potassium ethanoate and the acetic acid of manganous sulfate, Potcrate and the 1mol/L of 2 mol/L are added to the water, are stirred to and mix.Change over to then and have in the teflon-lined autoclave, behind 160 ℃ of reaction 12 h, after washing and filtering, oven dry, obtain the Manganse Dioxide overlong nanowire in the thermostat container.
Embodiment 2:
Potassium ethanoate and the acetic acid of manganous sulfate, Potcrate and the 1mol/L of 1 mol/L are added to the water, are stirred to and mix.Change over to then and have in the teflon-lined autoclave, behind 160 ℃ of reaction 12 h, after washing and filtering, oven dry, obtain the Manganse Dioxide overlong nanowire in the thermostat container.
Embodiment 3:
Potassium ethanoate and the acetic acid of manganous sulfate, Potcrate and 1.5 mol/L of 2 mol/L are added to the water, are stirred to and mix.Change over to then and have in the teflon-lined autoclave, behind 160 ℃ of reaction 12 h, after washing and filtering, oven dry, obtain the Manganse Dioxide overlong nanowire in the thermostat container.
Embodiment 4:
Potassium ethanoate and the acetic acid of manganous sulfate, Potcrate and 1.5 mol/L of 2 mol/L are added to the water, are stirred to and mix.Change over to then and have in the teflon-lined autoclave, behind 140 ℃ of reaction 12 h, after washing and filtering, oven dry, obtain the Manganse Dioxide overlong nanowire in the thermostat container.
Embodiment 5:
Potassium ethanoate and the acetic acid of manganous sulfate, Potcrate and 1.5 mol/L of 3 mol/L are added to the water, are stirred to and mix.Change over to then and have in the teflon-lined autoclave, behind 180 ℃ of reaction 12 h, after washing and filtering, oven dry, obtain the Manganse Dioxide overlong nanowire in the thermostat container.
Embodiment 6:
Potassium ethanoate and the acetic acid of manganous sulfate, Potcrate and 2 mol/L of 3 mol/L are added to the water, are stirred to and mix.Change over to then and have in the teflon-lined autoclave, behind 200 ℃ of reaction 12 h, after washing and filtering, oven dry, obtain the Manganse Dioxide overlong nanowire in the thermostat container.
Embodiment 7:
Potassium ethanoate and the acetic acid of manganous sulfate, Potcrate and 0.5 mol/L of 1 mol/L are added to the water, are stirred to and mix.Change over to then and have in the teflon-lined autoclave, behind 160 ℃ of reaction 6 h, after washing and filtering, oven dry, obtain the Manganse Dioxide overlong nanowire in the thermostat container.
Embodiment 8:
Potassium ethanoate and the acetic acid of manganous sulfate, Potcrate and the 1mol/L of 1 mol/L are added to the water, are stirred to and mix.Change over to then and have in the teflon-lined autoclave, behind 160 ℃ of reaction 24 h, after washing and filtering, oven dry, obtain the Manganse Dioxide overlong nanowire in the thermostat container.
Claims (5)
1. the preparation method of an overlength manganese dioxide nano line is characterized in that may further comprise the steps:
Be reductive agent manganous sulfate and the equimolar oxygenant chloric acid potassium of 1 ~ 3 mol/L with concentration, concentration is that the Potassium ethanoate of 0.5 ~ 1.5 mol/L and equimolar acetic acid are that additive is added to the water to stir and forms homogeneous solution, then carry out hydro-thermal reaction, after washing and filtering, oven dry, namely obtain overlength manganese dioxide nano line again.
2. preparation method according to claim 1, it is characterized in that: the volumetric molar concentration of described reductive agent manganous sulfate and oxygenant chloric acid potassium is 1.5 ~ 2 mol/L.
3. preparation method according to claim 1, it is characterized in that: the volumetric molar concentration of described additive Potassium ethanoate and acetic acid is 0.75 ~ 1 mol/L.
4. preparation method according to claim 1, it is characterized in that: described hydrothermal temperature is 140 ~ 200 ℃, the hydro-thermal reaction time is 6 ~ 24 h.
5. preparation method according to claim 4, it is characterized in that: described hydrothermal temperature is 160 ~ 180 ℃.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098141A (en) * | 2014-07-11 | 2014-10-15 | 陈秀琼 | Preparation method of hexagram-shaped alpha-MnO2 and ORR application of alpha-MnO2 |
| CN104098142A (en) * | 2014-07-11 | 2014-10-15 | 陈秀琼 | Preparation method of hexagram-shaped epsilon-MnO2 and ORR application of epsilon-MnO2 |
| CN104261478A (en) * | 2014-09-19 | 2015-01-07 | 济南大学 | Preparation method of Mn3O4 nanowire or nanorod |
| CN106098395A (en) * | 2016-06-02 | 2016-11-09 | 中南大学 | A kind of manganese dioxide fiber electrode and its preparation method and application |
| CN106745285A (en) * | 2017-03-01 | 2017-05-31 | 哈尔滨工业大学 | A kind of α MnO2The preparation method of nano wire |
| CN106939429A (en) * | 2017-03-15 | 2017-07-11 | 广东工业大学 | A kind of preparation method of new oxygen reduction electro-catalyst |
| CN106957068A (en) * | 2016-01-08 | 2017-07-18 | 新材料与产业技术北京研究院 | A kind of α-MnO2The preparation method of nano wire |
| CN107154311A (en) * | 2016-12-26 | 2017-09-12 | 广东工业大学 | A kind of preparation method and applications of orderly manganese dioxide nanowire thin-film electrode material |
| CN107434263A (en) * | 2017-07-25 | 2017-12-05 | 湖南电将军新能源有限公司 | The preparation method of 1-dimention nano line style manganate cathode material for lithium |
| CN107540023A (en) * | 2017-10-30 | 2018-01-05 | 重庆大学 | A kind of overlength manganese dioxide nanowire material and preparation method thereof |
| CN111808489A (en) * | 2020-07-07 | 2020-10-23 | 安徽新大陆特种涂料有限责任公司 | Production process of waterborne toughening paint containing metal nanowires |
| CN112167335A (en) * | 2020-10-13 | 2021-01-05 | 和县万谷粮油有限责任公司 | Processing technology for improving easy cracking of rice in storage environment |
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| WO2001087775A1 (en) * | 2000-05-15 | 2001-11-22 | Eveready Battery Company Inc. | A method of preparation of porous manganese dioxide |
| CN101798118A (en) * | 2010-03-11 | 2010-08-11 | 湘潭大学 | Preparation method of manganese dioxide one-dimensional nanomaterial |
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2013
- 2013-05-03 CN CN201310069196.5A patent/CN103193273B/en active Active
Patent Citations (3)
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| CN1051335A (en) * | 1990-11-21 | 1991-05-15 | 重庆干电池总厂 | The chemical manganese bioxide manufacture method |
| WO2001087775A1 (en) * | 2000-05-15 | 2001-11-22 | Eveready Battery Company Inc. | A method of preparation of porous manganese dioxide |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098141A (en) * | 2014-07-11 | 2014-10-15 | 陈秀琼 | Preparation method of hexagram-shaped alpha-MnO2 and ORR application of alpha-MnO2 |
| CN104098142A (en) * | 2014-07-11 | 2014-10-15 | 陈秀琼 | Preparation method of hexagram-shaped epsilon-MnO2 and ORR application of epsilon-MnO2 |
| CN104098141B (en) * | 2014-07-11 | 2016-05-04 | 雷伟强 | A kind of α-MnO of hexagonal star-shape2Preparation method and ORR application thereof |
| CN104098142B (en) * | 2014-07-11 | 2016-05-04 | 雷伟强 | A kind of ε-MnO of hexagonal star-shape2Preparation method and ORR application thereof |
| CN104261478A (en) * | 2014-09-19 | 2015-01-07 | 济南大学 | Preparation method of Mn3O4 nanowire or nanorod |
| CN106957068A (en) * | 2016-01-08 | 2017-07-18 | 新材料与产业技术北京研究院 | A kind of α-MnO2The preparation method of nano wire |
| CN106957068B (en) * | 2016-01-08 | 2018-06-29 | 新材料与产业技术北京研究院 | A kind of α-MnO2The preparation method of nano wire |
| CN106098395A (en) * | 2016-06-02 | 2016-11-09 | 中南大学 | A kind of manganese dioxide fiber electrode and its preparation method and application |
| CN107154311A (en) * | 2016-12-26 | 2017-09-12 | 广东工业大学 | A kind of preparation method and applications of orderly manganese dioxide nanowire thin-film electrode material |
| CN106745285A (en) * | 2017-03-01 | 2017-05-31 | 哈尔滨工业大学 | A kind of α MnO2The preparation method of nano wire |
| 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 |
| CN106939429A (en) * | 2017-03-15 | 2017-07-11 | 广东工业大学 | A kind of preparation method of new oxygen reduction electro-catalyst |
| CN107434263A (en) * | 2017-07-25 | 2017-12-05 | 湖南电将军新能源有限公司 | The preparation method of 1-dimention nano line style manganate cathode material for lithium |
| CN107540023A (en) * | 2017-10-30 | 2018-01-05 | 重庆大学 | A kind of overlength manganese dioxide nanowire material and preparation method thereof |
| CN107540023B (en) * | 2017-10-30 | 2019-04-26 | 重庆大学 | A kind of overlength manganese dioxide nanowire material and preparation method thereof |
| CN111808489A (en) * | 2020-07-07 | 2020-10-23 | 安徽新大陆特种涂料有限责任公司 | Production process of waterborne toughening paint containing metal nanowires |
| CN112167335A (en) * | 2020-10-13 | 2021-01-05 | 和县万谷粮油有限责任公司 | Processing technology for improving easy cracking of rice in storage environment |
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