CN102030371B - Preparation method of manganese dioxide nanowire with high aspect ratio - Google Patents
Preparation method of manganese dioxide nanowire with high aspect ratio Download PDFInfo
- Publication number
- CN102030371B CN102030371B CN 201010614448 CN201010614448A CN102030371B CN 102030371 B CN102030371 B CN 102030371B CN 201010614448 CN201010614448 CN 201010614448 CN 201010614448 A CN201010614448 A CN 201010614448A CN 102030371 B CN102030371 B CN 102030371B
- Authority
- CN
- China
- Prior art keywords
- manganese dioxide
- preparation
- diameter ratio
- manganse dioxide
- high length
- 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.)
- Expired - Fee Related
Links
Images
Abstract
The invention relates to a preparation method of a manganese dioxide nanowire with high aspect ratio, comprising the following steps of: preparing manganese dioxide sol-gel by taking potassium permanganate, reducing agent alcohol and inorganic acid as a pH-value regulator as raw materials; and cauterizing the obtained manganese dioxide dried gel fine-powders to synthesize the manganese dioxide nanowires with high aspect ratio after preparing manganese dioxide dried gel fine-powders from the prepared products of manganese dioxide sol-gel. In the invention, the prepared manganese dioxide nanowire consists of alpha-MnO2, wherein the content of the nanowires is larger than 90%, the diameter and the length of single nanowire are respectively 10-20 nm and 2.0-5.0 mum. By utilizing the method provided by the invention, the prepared alpha-MnO2 has high aspect ratio, purity and evenness; in addition, the preparation method has the advantages of no toxic effect or environment pollution and high utilization ratio of raw materials, and is important to the large-scale preparation and the industrial application of high-activity manganese dioxides.
Description
Technical field
The present invention relates to a kind of preparation method of manganese dioxide nano line of high length-diameter ratio.
Background technology
Manganse Dioxide is because its excellent electrochemical properties becomes a kind of electrode materials that is widely used.Micromorphologic research mainly concentrates in the preparation that the one dimension nano material of manganese dioxide is a wire Manganse Dioxide for Manganse Dioxide at present.Preparation manganese dioxide nano line comprises two big methods: hydrothermal method and sol-gel method.Wherein adopt the Prepared by Sol Gel Method manganese dioxide one-dimensional nano material and need not HTHP and advantage with short production cycle and that output is big in simple, synthetic, be easy to carry out suitability for industrialized production with respect to adopting hydrothermal method to have presoma.In addition on the one hand, the microtexture of Manganse Dioxide is the MnO that is shared by limit or angle
6The unit is formed, and the various combination mode has determined the different crystal forms of Manganse Dioxide, like α-MnO
2, β-MnO
2And δ-MnO
2Deng.The Manganse Dioxide of different crystal forms has the pore passage structure of different size, for example α-MnO simultaneously
22 * 2 pore passage structures, β-MnO
21 * 1 pore passage structure, and the different size of these pore passage structures has not only determined the specific surface area size of Manganse Dioxide also to determine different cationic existence in the pore passage structure.These reasons have determined the electrochemical activity of different crystal forms Manganse Dioxide to be not quite similar, and document shows [1], and that chemical property is best is α-MnO
2In sum, how to prepare α-MnO in a large number with sol-gel method
2The one dimension manganese bioxide material is the problem with realistic meaning.
[1]Y.L.Cao，H.X.Yang，X.P.Ai，L.F.Xiao.The?mechanism?of?oxygen?reduction?on?MnO
2-catalyzed?air?cathode?in?alkaline?solution[J].Journal?of?Electroanalytical?Chemistry，2003，557：127-134.
Summary of the invention
The invention discloses a kind of preparation method of manganese dioxide nano line of high length-diameter ratio, in order to realize preparing the best α-MnO of chemical property in a large number with sol-gel method
2One dimension high length-diameter ratio nano wire, the present invention has adopted following scheme:
A kind of preparation method of manganese dioxide nano line of high length-diameter ratio is characterized in that comprising the steps:
Step 1: with potassium permanganate, the pure and mild mineral acid as pH value regulator of reductive agent is raw material, preparation Manganse Dioxide gel;
1.1 analytical pure level potassium permanganate is dissolved in the deionized water, and stirring at room is to adding dilute nitric acid solution after the dissolving fully;
1.2 regulate the pH value in 5.7～6.6 scopes, stir;
1.3 add reductive agent alcohol, leave standstill after the violent stirring in short-term, this mixing solutions forms jelly shape monolithic dark-brown Manganse Dioxide gel after two minutes;
1.4 with still aging 12～20 hours of Manganse Dioxide gel;
Step 2: the jel product of Manganse Dioxide described in the step 1 is prepared into Manganse Dioxide xerogel fine powder;
2.1 with the Manganse Dioxide gel spinning after the ageing;
2.2 the removal supernatant liquid carries out vacuum-drying and forms the Manganse Dioxide xerogel after solid taken out from centrifuge tube;
2.3 obtain Manganse Dioxide xerogel black fine powder after grinding the Manganse Dioxide xerogel;
Step 3: the xerogel of Manganse Dioxide described in the step 2 fine powder is burnt the manganese dioxide nano line of synthetic high length-diameter ratio.
The amount of substance concentration of analytical pure level potassium permanganate is 0.05～0.2mol/L in the said step 1.
The amount of substance concentration of rare nitric acid is 0.1～1mol/L in the said step 1.
The standard that adds reductive agent alcohol in the said step 1 is that the hydroxyl of reductive agent alcohol and the mol ratio of potassium permanganate are 140～240: 1.
Said reductive agent alcohol is ethanol.
The spinning condition of said step 2 is 2000-10000 rev/min.
Vacuum drying temperature and vacuum drying time are respectively 70 ℃～120 ℃ and 10～20 hours in the said step 2.
The air atmosphere that burns black Manganse Dioxide xerogel fine powder in the said step 3 is 450 ℃～520 ℃.
The time of burning black Manganse Dioxide xerogel fine powder in the said step 3 is 2～5 hours.
A kind ofly make manganese dioxide nano line product according to the said preparation method of claim 1 to 9, it is by α-MnO
2Form, wherein nano wire content is greater than 90%, and the single nano-wire diameter is 10-20nm, and length is 2.0-5.0 μ m.
The present invention has following beneficial effect:
(1) crystal formation of the manganese dioxide product that makes of the present invention is the α type, and its chemical property is good, and microscopic pattern is the nano wire of high length-diameter ratio and does not have impure impurity.
(2) the present invention prepares the α-MnO of high length-diameter ratio
2The sol-gel method technology that nano wire adopts is simple, except that alcohols material, without other additive, is applicable to a large amount of preparations of Manganse Dioxide.
(3) α-MnO
2Medicine nontoxic pollution-free that adopts in the preparation process of nano wire and utilization ratio are high, are environmentally friendly processes.
Description of drawings
Fig. 1 high length-diameter ratio Manganse Dioxide provided by the invention α-MnO
2The X-ray diffraction spectrogram of nano wire.
The high length-diameter ratio Manganse Dioxide α-MnO of Fig. 2 embodiment 1 preparation
2The electron scanning micrograph of nano wire.
Embodiment
The several embodiment of various details further understand the present invention.
Employed all reagent are all bought in the Beijing Chemical Plant among the following embodiment.
Embodiment 1
1) analytical pure level potassium permanganate is dissolved in (amount of substance concentration is 0.12mol/L) in the deionized water; Stirring at room is the dilute nitric acid solution of 0.1mol/L to dissolving back adding amount of substance concentration fully, and regulating pH value is 5.7, after stirring; In the mol ratio of hydroxyl and potassium permanganate is that 140: 1 ratio adds alcohol; Leave standstill after the violent stirring in short-term, this mixing solutions forms jelly shape monolithic dark-brown gel after about two minutes, with this gel continue still aging 12 hours for use;
2) gel after the ageing is centrifugal under 2000 rev/mins of conditions, from centrifuge tube, take out the back and formed the Manganse Dioxide xerogel in 10 hours 70 ℃ of following vacuum-dryings, obtain the black fine powder after the grinding;
3) take out the black fine powder is burnt 2 hours in 450 ℃ of air atmospheres after and obtain α-MnO
2Product, diameter are 10nm, and length is 2.0 μ m, and average aspect ratio is 200.Accompanying drawing 2 has provided the electron scanning micrograph of this product.
Embodiment 2
1) analytical pure level potassium permanganate is dissolved in (amount of substance concentration is 0.1mol/L) in the deionized water; Stirring at room is the dilute nitric acid solution of 0.5mol/L to dissolving back adding amount of substance concentration fully, and regulating pH value is 6.2, after stirring; In the mol ratio of hydroxyl and potassium permanganate is that 200: 1 ratio adds alcohol; Leave standstill after the violent stirring in short-term, this mixing solutions forms jelly shape monolithic dark-brown gel after about two minutes, with this gel continue still aging 15 hours for use;
2) gel after the ageing is centrifugal under 5000 rev/mins of conditions, from centrifuge tube, take out the back and formed the Manganse Dioxide xerogel in 15 hours 90 ℃ of following vacuum-dryings, obtain the black fine powder after the grinding;
3) take out the black fine powder is burnt 3 hours in 500 ℃ of air atmospheres after and obtain α-MnO
2Product, diameter are 12nm, and length is 4.2 μ m, and average aspect ratio is 350.
Embodiment 3
1) analytical pure level potassium permanganate is dissolved in (amount of substance concentration is 0.2mol/L) in the deionized water; Stirring at room is the dilute nitric acid solution of 1mol/L to dissolving back adding amount of substance concentration fully, and regulating pH value is 6.6, after stirring; In the mol ratio of hydroxyl and potassium permanganate is that 240: 1 ratio adds alcohol; Leave standstill after the violent stirring in short-term, this mixing solutions forms jelly shape monolithic dark-brown gel after about two minutes, with this gel continue still aging 20 hours for use;
2) gel after the ageing is centrifugal under 2000-10000 rev/min of condition, from centrifuge tube, take out the back and formed the Manganse Dioxide xerogel in 20 hours 120 ℃ of following vacuum-dryings, obtain the black fine powder after the grinding;
3) take out the black fine powder is burnt 5 hours in 520 ℃ of air atmospheres after and obtain α-MnO
2Product, diameter are 20nm, and length is 5 μ m, and average aspect ratio is 250.
Above the present invention has been carried out exemplary description; Obvious realization of the present invention does not receive the restriction of aforesaid way; As long as the various improvement of having adopted method design of the present invention and technical scheme to carry out; Or design of the present invention and technical scheme are directly applied to other occasion without improving, all in protection scope of the present invention.
Claims (10)
1. the preparation method of the manganese dioxide nano line of a high length-diameter ratio is characterized in that comprising the steps:
Step 1: with potassium permanganate, the pure and mild mineral acid as pH value regulator of reductive agent is raw material, preparation Manganse Dioxide gel;
1.1 analytical pure level potassium permanganate is dissolved in the deionized water, and stirring at room is to adding dilute nitric acid solution after the dissolving fully;
1.2 regulate the pH value in 5.7～6.6 scopes, stir;
1.3 add reductive agent alcohol, leave standstill after the violent stirring in short-term, this mixing solutions forms jelly shape monolithic dark-brown Manganse Dioxide gel after two minutes;
1.4 with still aging 12～20 hours of Manganse Dioxide gel;
Step 2: the jel product of Manganse Dioxide described in the step 1 is prepared into Manganse Dioxide xerogel fine powder;
2.1 with the Manganse Dioxide gel spinning after the ageing;
2.2 the removal supernatant liquid carries out vacuum-drying and forms the Manganse Dioxide xerogel after solid taken out from centrifuge tube;
2.3 obtain Manganse Dioxide xerogel black fine powder after grinding the Manganse Dioxide xerogel;
Step 3: the xerogel of Manganse Dioxide described in the step 2 fine powder is burnt the manganese dioxide nano line of synthetic high length-diameter ratio.
2. according to the preparation method of the said high length-diameter ratio manganese dioxide nano of claim 1 line, it is characterized in that: the amount of substance concentration of analytical pure level potassium permanganate is 0.05～0.2mol/L in the said step 1.
3. according to the preparation method of claim 1 or 2 said high length-diameter ratio manganese dioxide nano lines, it is characterized in that: the amount of substance concentration of rare nitric acid is 0.1～1mol/L in the said step 1.
4. according to the preparation method of the said high length-diameter ratio manganese dioxide nano of claim 3 line, it is characterized in that: the standard that adds reductive agent alcohol in the said step 1 is that the hydroxyl of reductive agent alcohol and the mol ratio of potassium permanganate are 140～240: 1.
5. according to the preparation method of any one said high length-diameter ratio manganese dioxide nano line in the claim 1,2 or 4, it is characterized in that: said reductive agent alcohol is ethanol.
6. according to the preparation method of the said high length-diameter ratio manganese dioxide nano of claim 5 line, it is characterized in that: the spinning condition of said step 2 is 2000-10000 rev/min.
7. according to the preparation method of the said high length-diameter ratio manganese dioxide nano of claim 6 line, it is characterized in that: vacuum drying temperature and vacuum drying time are respectively 70 ℃～120 ℃ and 10～20 hours in the said step 2.
8. according to the preparation method of the said high length-diameter ratio manganese dioxide nano of claim 7 line, it is characterized in that: the air atmosphere that burns black Manganse Dioxide xerogel fine powder in the said step 3 is 450 ℃～520 ℃.
9. the preparation method of said according to Claim 8 high length-diameter ratio manganese dioxide nano line is characterized in that: the time of burning black Manganse Dioxide xerogel fine powder in the said step 3 is 2～5 hours.
10. one kind makes manganese dioxide nano line product according to any one said preparation method in the claim 1 to 9, and it is characterized in that: it is by α-MnO
2Form, wherein nano wire content is greater than 90%, and the single nano-wire diameter is 10-20nm, and length is 2.0-5.0 μ m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010614448 CN102030371B (en) | 2010-12-21 | 2010-12-21 | Preparation method of manganese dioxide nanowire with high aspect ratio |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010614448 CN102030371B (en) | 2010-12-21 | 2010-12-21 | Preparation method of manganese dioxide nanowire with high aspect ratio |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102030371A CN102030371A (en) | 2011-04-27 |
| CN102030371B true CN102030371B (en) | 2012-07-25 |
Family
ID=43883896
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010614448 Expired - Fee Related CN102030371B (en) | 2010-12-21 | 2010-12-21 | Preparation method of manganese dioxide nanowire with high aspect ratio |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102030371B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101395361B1 (en) * | 2011-05-02 | 2014-05-14 | 삼성코닝정밀소재 주식회사 | Method of producing Manganese Oxide nano-wire |
| CN102336442B (en) * | 2011-06-30 | 2013-07-17 | 上海大学 | K0.125MnO2 nanowire and preparation method thereof |
| CN102689929A (en) * | 2012-06-12 | 2012-09-26 | 东华大学 | Method for preparing ultralong MnO2 nanowire supercapacitor material |
| CN104628039B (en) * | 2015-02-06 | 2016-04-27 | 南京工业大学 | A kind of controllable method for preparing of α-manganese dioxide nanowire |
| 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 |
| CN105502504A (en) * | 2016-02-17 | 2016-04-20 | 上海应用技术学院 | Preparation method of manganese dioxide nanowire |
| 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 |
| CN109148877A (en) * | 2018-07-30 | 2019-01-04 | 桑顿新能源科技有限公司 | Rechargeable zinc-manganese battery and preparation method thereof |
| CN113053675B (en) * | 2021-03-11 | 2023-07-28 | 深圳今为科技有限公司 | Preparation method of electrode composite material applied to super capacitor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597086A (en) * | 2009-06-26 | 2009-12-09 | 海南大学 | Method for preparing nano manganese dioxide with different crystal forms in low-temperature acid solution |
-
2010
- 2010-12-21 CN CN 201010614448 patent/CN102030371B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597086A (en) * | 2009-06-26 | 2009-12-09 | 海南大学 | Method for preparing nano manganese dioxide with different crystal forms in low-temperature acid solution |
Non-Patent Citations (4)
| Title |
|---|
| Suk Fun Chin et al.Self-assembled manganese dioxide nanowires as electrode materials for electrochemical capacitors.《Materials letters》.2010,第64卷 * |
| Xingyan Wang et al.Sol–gel template synthesis of highly ordered MnO2 nanowire arrays.《Journal of Power Sources》.2004,第140卷 * |
| 努尔买买提等.纳米α-MnO2的制备及其性能研究.《无机材料学报》.2000,第15卷(第5期), * |
| 马淳安等.纳米MnO2的制备及电化学性能研究.《中国有色金属学报》.2004,第14卷(第10期), * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102030371A (en) | 2011-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102030371B (en) | Preparation method of manganese dioxide nanowire with high aspect ratio | |
| CN103193273B (en) | Preparation method of extra-long manganese dioxide nanowires | |
| Zhou et al. | Controllable synthesis of three-dimensional well-defined BiVO4 mesocrystals via a facile additive-free aqueous strategy | |
| Kadam et al. | Biogenic synthesis of mesoporous N–S–C tri-doped TiO2 photocatalyst via ultrasonic-assisted derivatization of biotemplate from expired egg white protein | |
| CN102120619B (en) | Preparation method of brain-coral-shaped birnessite type manganese dioxide | |
| EP3617147B1 (en) | Process for preparing titanic acid salt, titanic acid, and titanium oxide having controllable particle size and hierarchical structure | |
| Li et al. | Niobium pentoxide hollow nanospheres with enhanced visible light photocatalytic activity | |
| CN107579241B (en) | Preparation method of three-dimensional tent type graphene-metal oxide nano composite material | |
| CN104150528A (en) | Preparation method of doped stannic oxide conductive nano powder | |
| Rasheed et al. | Synthesis and studies of ZnO doped with g-C3N4 nanocomposites for the degradation of tetracycline hydrochloride under the visible light irradiation | |
| CN105621474A (en) | Hyperbranched graded cuprous oxide nanomateiral and preparation method and application thereof | |
| Liu et al. | Soluble starch-modulated solvothermal synthesis of grain-like Bi24O31Br10 hierarchical architectures with enhanced photocatalytic activity | |
| CN105883939A (en) | Preparation method for nickel sulfide/graphene/carbon nano tube/cobalt sulfide three-dimensional composite hydrogen storage material | |
| CN103754935B (en) | Method for synthesizing lead molybdate tower crystal at room temperature | |
| CN102826603A (en) | Preparation method of vanadium pentoxide nanofibers | |
| CN103933957B (en) | Porous monocrystalline nano titanium dioxide photocatalyst that a kind of high crystallization, size are controlled, high-energy surface exposes and its preparation method and application | |
| CN109326791B (en) | Linear porous lithium titanate material and preparation and product thereof | |
| CN106006717A (en) | Preparing method of ZnS nano aerogel | |
| CN109231276A (en) | Sulfamic acid restores potassium permanganate and prepares α-MnO2The method and application of nano wire | |
| Farid et al. | Fabrication and characterization of MnO2 based composite sheets for development of flexible energy storage electrodes | |
| CN104310306A (en) | High-sensitivity alcohol-sensitive gas sensor, preparation method thereof, and preparation method of mesoporous SnO2 material | |
| CN103588244B (en) | Without the method for the sandwich hollow titanium dioxide nano material of template synthesis | |
| CN108373172B (en) | Preparation method of manganese oxide one-dimensional nanowire | |
| CN102716735B (en) | Preparation method of ATP/ Ce-Ti sold soluble oxide composite material | |
| CN105502504A (en) | Preparation method of manganese dioxide nanowire |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120725 Termination date: 20181221 |