CN103193273B - Preparation method of extra-long manganese dioxide nanowires - Google Patents
Preparation method of extra-long manganese dioxide nanowires Download PDFInfo
- Publication number
- CN103193273B CN103193273B CN201310069196.5A CN201310069196A CN103193273B CN 103193273 B CN103193273 B CN 103193273B CN 201310069196 A CN201310069196 A CN 201310069196A CN 103193273 B CN103193273 B CN 103193273B
- Authority
- CN
- China
- Prior art keywords
- manganese dioxide
- preparation
- mol
- extra
- acetic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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 again superior electrochemistry and magnetic performance simultaneously, can be used as positive electrode material and the novel magnetic material of lithium ion battery.The simultaneously special character of nano material, such as one dimension manganese dioxide nano line is conducive to the conduction of electronics.As the manganese dioxide nano line of existing document Britain " chemical communication " (Chemical Communications, 2011 4 phase 1264 pages) report one dimension can be for ultracapacitor.And there is the document U.S. " nanometer wall bulletin " (Nano Letters, 2010 10 phase 3852 pages) the report manganese dioxide nano line also can be for the preparation of lithium manganate nano-material.
The preparation method who prepares at present manganese dioxide nano line is many, 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, and purity is high, the nano wire of even size distribution Manganse Dioxide, and reproducible; But vapour deposition process generally needs pyroreaction, this has also just determined that it is higher to equipment requirements, invests greatlyr, and operational condition is harsher etc.Liquid phase method reaction conditions is easily realized comparatively speaking, and can add a lot of additives and regulate and control the growth of manganese dioxide nano line, therefore Liquid preparation methods manganese dioxide nano lines that adopt now more.But except hydrothermal method, general liquid phase method all needs through high-temperature calcination, and this not only consumes mass energy, and products therefrom is easily reunited, cause distribution of sizes inhomogeneous, sol-gel method as used in Chinese patent 201010614448.4 is prepared the just further calcining of needs of manganese dioxide nano line.Hydro-thermal reaction is to carry out under non-confined condition, has reaction conditions close friend compared with other wet chemistry methods, and low temperature do not need calcining can directly in solution, obtain product, and product purity is high, the advantages such as even size distribution.Prepare manganese dioxide nano line about hydrothermal method, existing document Germany " advanced material " (Advanced Materials, 2004 19 phase 1729 pages) report to some extent.Also there is part Chinese patent to report manganese dioxide nano line simultaneously, as 02100707.1,200510014876.2,201210193021.0 etc.
But at present method all cannot be prepared the manganese dioxide nano line that length is greater than 100 μ m under mild conditions, and not yet there are document or patent report taking the preparation that acetic acid and Potassium ethanoate are controlled Manganse Dioxide overlong nanowire as additive.While growth for growth material in view of acetate ion, there is to provide protection side, in this patent, we,, taking acetic acid and Potassium ethanoate as additive, have prepared overlength manganese dioxide nano line under hydrothermal condition.
Summary of the invention
The present invention's object 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 preparation method for overlength manganese dioxide nano line, comprises the following steps:
Be reductive agent manganous sulfate and the equimolar oxygenant chloric acid potassium of 1 ~ 3 mol/L by 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, then can obtain overlength manganese dioxide nano line after washing and filtering, oven dry.
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 DEG C, and the hydro-thermal reaction time is 6 ~ 24 h.
The method is taking manganous sulfate as reductive agent, and Potcrate is oxygenant, and taking Potassium ethanoate and acetic acid as additive, in teflon-lined autoclave, hydro-thermal reaction 6 ~ 24 h at 140 ~ 200 DEG C, can obtain overlength manganese dioxide nano line.
For further realizing the present invention, described hydrothermal temperature is preferably at 160 ~ 180 DEG C, and described reductive agent and the concentration of oxygenant are 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 preparation method who the invention provides a kind of overlength manganese dioxide nano line has environmental friendliness compared with other wet chemistry methods, and 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, between 50 ~ 150 nm, is evenly distributed, and rich surface is conducive to further modification containing a large amount of hydroxyls.
Brief description of the drawings
The XRD spectra of manganese dioxide nano line prepared by Fig. 1 embodiment of the present invention 2.
The scanning electron microscope (SEM) photograph of manganese dioxide nano line prepared by Fig. 2 embodiment of the present invention 4.
The transmission electron microscope picture of manganese dioxide nano line prepared by Fig. 3 embodiment of the present invention 7.
embodiment:
Embodiment 1:
The Potassium ethanoate of the manganous sulfate of 2 mol/L, Potcrate and 1mol/L and acetic acid are added to the water, are stirred to and mix.Then proceed to in teflon-lined autoclave, in thermostat container, after 160 DEG C of reaction 12 h, after washing and filtering, oven dry, obtain Manganse Dioxide overlong nanowire.
Embodiment 2:
The Potassium ethanoate of the manganous sulfate of 1 mol/L, Potcrate and 1mol/L and acetic acid are added to the water, are stirred to and mix.Then proceed to in teflon-lined autoclave, in thermostat container, after 160 DEG C of reaction 12 h, after washing and filtering, oven dry, obtain Manganse Dioxide overlong nanowire.
Embodiment 3:
Potassium ethanoate and the acetic acid of the manganous sulfate of 2 mol/L, Potcrate and 1.5 mol/L are added to the water, are stirred to and mix.Then proceed to in teflon-lined autoclave, in thermostat container, after 160 DEG C of reaction 12 h, after washing and filtering, oven dry, obtain Manganse Dioxide overlong nanowire.
Embodiment 4:
The Potassium ethanoate of the manganous sulfate of 2 mol/L, Potcrate and 1.5 mol/L and acetic acid are added and is added to the water, be stirred to and mix.Then proceed to in teflon-lined autoclave, in thermostat container, after 140 DEG C of reaction 12 h, after washing and filtering, oven dry, obtain Manganse Dioxide overlong nanowire.
Embodiment 5:
Potassium ethanoate and the acetic acid of the manganous sulfate of 3 mol/L, Potcrate and 1.5 mol/L are added to the water, are stirred to and mix.Then proceed to in teflon-lined autoclave, in thermostat container, after 180 DEG C of reaction 12 h, after washing and filtering, oven dry, obtain Manganse Dioxide overlong nanowire.
Embodiment 6:
Potassium ethanoate and the acetic acid of the manganous sulfate of 3 mol/L, Potcrate and 2 mol/L are added to the water, are stirred to and mix.Then proceed to in teflon-lined autoclave, in thermostat container, after 200 DEG C of reaction 12 h, after washing and filtering, oven dry, obtain Manganse Dioxide overlong nanowire.
Embodiment 7:
Potassium ethanoate and the acetic acid of the manganous sulfate of 1 mol/L, Potcrate and 0.5 mol/L are added to the water, are stirred to and mix.Then proceed to in teflon-lined autoclave, in thermostat container, after 160 DEG C of reaction 6 h, after washing and filtering, oven dry, obtain Manganse Dioxide overlong nanowire.
Embodiment 8:
The Potassium ethanoate of the manganous sulfate of 1 mol/L, Potcrate and 1mol/L and acetic acid are added to the water, are stirred to and mix.Then proceed to in teflon-lined autoclave, in thermostat container, after 160 DEG C of reaction 24 h, after washing and filtering, oven dry, obtain Manganse Dioxide overlong nanowire.
Claims (4)
1. a preparation method for overlength manganese dioxide nano line, is characterized in that comprising the following steps:
Be reductive agent manganous sulfate and the equimolar oxygenant chloric acid potassium of 1 ~ 3 mol/L by 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, more obtain overlength manganese dioxide nano line after washing and filtering, oven dry; Described hydrothermal temperature is 140 ~ 200 DEG C, and the hydro-thermal reaction time is 6 ~ 24 h.
2. preparation method according to claim 1, 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, 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, is characterized in that: described hydrothermal temperature is 160 ~ 180 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310069196.5A CN103193273B (en) | 2013-05-03 | 2013-05-03 | Preparation method of extra-long manganese dioxide nanowires |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310069196.5A CN103193273B (en) | 2013-05-03 | 2013-05-03 | Preparation method of extra-long manganese dioxide nanowires |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103193273A CN103193273A (en) | 2013-07-10 |
| CN103193273B true CN103193273B (en) | 2014-07-16 |
Family
ID=48716119
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310069196.5A Active CN103193273B (en) | 2013-05-03 | 2013-05-03 | Preparation method of extra-long manganese dioxide nanowires |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103193273B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104261478B (en) * | 2014-09-19 | 2016-09-14 | 济南大学 | A kind of Mn3o4nano wire or the preparation method of nanometer rods |
| 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 |
| CN106098395B (en) * | 2016-06-02 | 2018-05-08 | 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 |
| 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 |
| CN107540023B (en) * | 2017-10-30 | 2019-04-26 | 重庆大学 | A kind of overlength manganese dioxide nanowire material and preparation method thereof |
| CN111808489B (en) * | 2020-07-07 | 2021-11-16 | 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101798118A (en) * | 2010-03-11 | 2010-08-11 | 湘潭大学 | Preparation method of manganese dioxide one-dimensional nanomaterial |
-
2013
- 2013-05-03 CN CN201310069196.5A patent/CN103193273B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101798118A (en) * | 2010-03-11 | 2010-08-11 | 湘潭大学 | Preparation method of manganese dioxide one-dimensional nanomaterial |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103193273A (en) | 2013-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103193273B (en) | Preparation method of extra-long manganese dioxide nanowires | |
| CN1333474C (en) | Preparation method of spinel lithium titanate nano tube/wire for lithium battery and capacitor | |
| CN107195896B (en) | A kind of preparation method synthesizing silicium cathode material using conductive metal nano particle as carrier low temperature | |
| CN102030371B (en) | Preparation method of manganese dioxide nanowire with high aspect ratio | |
| CN102010004A (en) | Method for preparing vanadium disulphide nano powder | |
| CN103523824B (en) | The preparation method of nano-sheet ferroelectric material for a kind of photocatalysis | |
| CN103130276B (en) | Preparation method of cadmium vanadate nanorods | |
| CN106745231B (en) | A kind of taper titanium dioxide nano-rod and preparation method thereof | |
| CN108288703A (en) | A kind of preparation method and applications of graphene coated fluorine doped lithium titanate nano wire | |
| CN105129849A (en) | Flowerlike nano-sized titanium dioxide material and template-free preparation method thereof | |
| CN101805009B (en) | Simple and controllable method for preparing lobate micron/nano copper oxide two-dimensional assembly | |
| Li et al. | TEA-assisted synthesis of single-crystalline Mn3O4 octahedrons and their magnetic properties | |
| CN107803170A (en) | A kind of preparation method of titanium dioxide/nickel oxide bivalve hollow ball | |
| CN103435097A (en) | Preparation method and application of nano zirconia | |
| CN105060352B (en) | A kind of preparation method of nickel oxide nano sheet/titanium dioxide nano-rod heterojunction material | |
| CN107032406B (en) | A kind of micro-nano beam of manganese molybdate and preparation method thereof | |
| CN104183827A (en) | Lithium iron phosphate nanorods and preparation method thereof | |
| CN107317019B (en) | Ferrous carbonate/graphene composite material for sodium ion battery cathode and preparation method and application thereof | |
| CN103833080B (en) | A kind of preparation method of molybdic acid cadmium porous ball | |
| CN103101964A (en) | Preparation method of zinc oxide nanoflower of spiauterite structure | |
| CN103060872B (en) | Method for preparing lignin sulfonate-doped nano-zinc oxide composite film by electrochemical deposition method | |
| CN103588244B (en) | Without the method for the sandwich hollow titanium dioxide nano material of template synthesis | |
| CN102079539B (en) | ZnO nano powder in sheet uniform porous structure as well as preparation method and applications thereof | |
| CN109517217B (en) | Tungsten-doped vanadium dioxide/graphene composite and preparation method and application thereof | |
| CN106915773A (en) | A kind of preparation method of strontium molybdate skeleton |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |