CN1686826A - Method for synthesizing nano material of manganese dioxide in dandelion and stick shape - Google Patents
Method for synthesizing nano material of manganese dioxide in dandelion and stick shape Download PDFInfo
- Publication number
- CN1686826A CN1686826A CN 200510043204 CN200510043204A CN1686826A CN 1686826 A CN1686826 A CN 1686826A CN 200510043204 CN200510043204 CN 200510043204 CN 200510043204 A CN200510043204 A CN 200510043204A CN 1686826 A CN1686826 A CN 1686826A
- Authority
- CN
- China
- Prior art keywords
- nano material
- manganese dioxide
- manganese
- synthetic method
- dissolved
- 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.)
- Granted
Links
Images
Abstract
The present invention provides a method for sythesizing taraxacum-shaped and rod-shaped manganese dioxide nano material. The method for synthesizing taraxacum-shaped nano material includes the following steps: adding hydrogen peroxide solution in soluble salt solution in which the divalent manganese in dissolved, stirring them and placing them into a reactor, heating, after the reaction is completed, cooling to room temperature, washing and drying so as to obtain the taraxacum-shaped manganese dioxide nano material. The method for synthesizing rod-shaped nano material includes the following steps: adding hydrogen peroxide solution in soluble salt solution in which the divalent manganese is dissolved, stirring, slowly adding weakly alkaline aqueous solution, making precipitation, placing them into a reactor, heating, after the reaction is completed, cooling to room temperature, washing and drying so as to obtain the rod-shaped nano material.
Description
Technical field
The present invention relates to field of inorganic chemical engineering, relate in particular to the synthetic method of three-dimensional taraxacum shape and one-dimensional rod-like nano material of manganese dioxide.
Background technology
The oxide-based nanomaterial of transition metal (Fe, Co, Ni, Mn etc.) has character such as special light, electricity, heat, magnetic because of it, be an important directions of nanometer material science research and discovery.Wherein, MnO
2Useful as catalysts, molecular sieve especially have very important application in field of chemical power source, as: as alkaline Mn cell positive electrode material, high-energy-density anode material of lithium battery etc.Bach etc. [S.Bach, M.Heny, N.Baffer, J.Livage, J.Solid State Chem.1990,88,325] point out that the electrochemical properties of Manganse Dioxide depends on parameters such as pattern, crystalline structure, bulk density to a great extent.And, may produce novel character along with size, shape and the dimension etc. of nano material are different.Thereby the nano material of manganese dioxide of preparation different-shape has important practical significance undoubtedly.At MnO
2The preparation aspect of nano material, people have carried out a large amount of work, except nano particle, have also synthesized the monodimension nanometer material of different compositions and different-shape: prepare acicular-MnO as circumfluence method
2[N.Kijima, H.Yasuda, T.Sato, Y.Yoshimura, J.Solid State Chem., 2001,159,94]; Sol-gel method prepares needle-like δ-MnO
2[F.A.Al-Sagheer, M.I.Zaki, Colloids Surf A, 2000,173,193]; Usefulness sol-gel processings such as Sugantha have prepared α-MnO in the presence of template
2Nanometer rod [M.Sugantha, PA.Ramakrishnan, A.M.Hermanm, Int.J.Hydrogen Energy 2003,28,597], [{ Mn (SO such as Xie Yi
4) (4,4 '-bby) (H
2O)
2}
n] prepared γ-MnO with the NaOH hydro-thermal reaction
2Nano wire [Y.Xiong, Y.Xie, Z.Li, C.Wu, Chem.Eur.J.2003,9,1645], Li Yadong utilizes MnSO
4With KMnO
4(or (NH
4)
2S
2O
8) the hydrothermal oxidization prepared in reaction α-MnO
2Nano wire and β-MnO
2Nanometer rod [X.Wang, Y.D.Li, J.Am.Chem.Soc.2002,124,2880].But simultaneously to β-MnO
2Pattern and the problem accurately controlled of crystal formation be not resolved yet.Three-dimensional MnO
2The preparation of nano material is also rarely found, and nearest Xie Yi etc. utilizes MnSO
4With KBrO
3Hydro-thermal reaction in the presence of polymer P VP or PEG, prepared sisal shape γ-MnO
2Nano material [C.Z.Wu, Y.Xie, D.Wang, J.Yang and T.W.Li, J.Phys.Chem.B, 2003,107,13583].And, do not find three-dimensional β-MnO at present as yet
2Preparation of nanomaterials.
Summary of the invention
The purpose of this invention is to provide that a kind of technology is simple without any need for tensio-active agent or template, cost is low, helps the three-dimensional taraxacum shape that large-scale industrial produces and the synthetic method of one-dimensional rod-like nano material of manganese dioxide.
Purpose of the present invention can realize by following technical measures:
In being dissolved with the soluble salt solution of bivalent manganese, add superoxol, stir, after insert in the reactor, heating reaction down finishes, and is cooled to room temperature then, again through washing and dry, three-dimensional taraxacum shape nano material of manganese dioxide.
In being dissolved with the soluble salt solution of bivalent manganese, add superoxol, stir, slowly add the weakly alkaline aqueous solution then, post precipitation to be generated is inserted in the reactor, and heating reaction down finishes, be cooled to room temperature again, after washing and dry gets the one-dimensional rod-like nano material of manganese dioxide.
The purpose of invention also can realize by following technical measures:
The preferred ammoniacal liquor of described weak base, Tri N-Propyl Amine, n-Butyl Amine 99, hexamethylenetetramine; The described preferred manganous nitrate of soluble salt solution of bivalent manganese, the aqueous solution of manganous sulfate of being dissolved with; Described temperature of reaction is 150-260 ℃, and the reaction times is 3-15 hour.
Stirring of the present invention was generally 5-30 minute; Described drying adopts conventional vacuum-drying usually; Described washing is to adopt the unreacted unnecessary ion of deionized water eccysis.
The present invention is a raw material with soluble salt solution, hydrogen peroxide and the weakly alkaline aqueous solution of bivalent manganese, by the hydro-thermal reaction of simple controllable, has prepared three-dimensional taraxacum shape and one-dimensional rod-like nano material of manganese dioxide.Avoided the introducing of tensio-active agent or template in this reaction process, simple to operate, the product purity height helps large-scale industrial production.The present invention has gone back systematic research preparation technology and condition adopt technology such as XRD, TEM, SEM that products obtained therefrom is characterized to the influence of product purity and pattern.
Description of drawings:
Fig. 1 is the XRD figure of the three-dimensional taraxacum shape nano material of manganese dioxide for preparing of the present invention;
Fig. 2 is the XRD figure of the one-dimensional rod-like nano material of manganese dioxide for preparing of the present invention;
Fig. 3 is the SEM figure of the three-dimensional taraxacum shape nano material of manganese dioxide for preparing of the present invention;
Fig. 4 is the TEM figure of the three-dimensional taraxacum shape nano material of manganese dioxide for preparing of the present invention;
Fig. 5 is the TEM figure of the one-dimensional rod-like nano material of manganese dioxide for preparing of the present invention;
Fig. 6 is the TEM figure of the one-dimensional rod-like nano material of manganese dioxide for preparing of the present invention.
Embodiment:
Embodiment 1:
In the aqueous solution of 10ml 70% manganous nitrate, add the 8ml30% superoxol, stirred 5 minutes, transfer in the stainless steel cauldron and reacted 12 hours under 180 ℃, reaction product is cooled to room temperature, at last black precipitate is got product with deionized water wash and 80 ℃ of following conventional vacuum-dryings.Product is a β attitude Manganse Dioxide through X-ray powder diffraction, and SEM testing product pattern is three-dimensional taraxacum shape.
Embodiment 2:
In the aqueous solution of 13ml3mol/L manganous sulfate, add the 5ml30% superoxol, stirred 20 minutes, transfer in the stainless steel cauldron and reacted 3 hours under 260 ℃, reaction product is cooled to room temperature, at last black precipitate is got product with deionized water wash and 60 ℃ of following conventional vacuum-dryings.Product is a β attitude Manganse Dioxide through X-ray powder diffraction, and SEM testing product pattern is three-dimensional taraxacum shape.
Embodiment 3:
In 12ml 0.5mol/L manganese nitrate aqueous solution, add the 2ml30% superoxol, stirred 10 minutes, the ammoniacal liquor or the Tri N-Propyl Amine aqueous solution or the n-Butyl Amine 99 aqueous solution or the hexamethylenetetramine aqueous solution that dropwise add 5ml0.5mol/L, after reaction is finished gained precipitation transferred in the stainless steel cauldron 150 ℃ of reactions 15 hours down, reaction product is cooled to room temperature, at last black precipitate is got product with deionized water wash and 40 ℃ of following conventional vacuum-dryings.Product is a β attitude Manganse Dioxide through X-ray powder diffraction, and TEM testing product pattern is an one-dimensional rod-like.
Embodiment 4:
In the aqueous solution of 12ml0.5mol/L manganous sulfate, add the 2ml30% superoxol, stirred 15 minutes, the ammoniacal liquor or the Tri N-Propyl Amine aqueous solution or the n-Butyl Amine 99 aqueous solution or the hexamethylenetetramine aqueous solution that dropwise add 5ml0.5mol/L, after reaction is finished gained precipitation transferred in the stainless steel cauldron 200 ℃ of reactions 8 hours down, reaction product is cooled to room temperature, at last black precipitate is got product with deionized water wash and 70 ℃ of following conventional vacuum-dryings.Product is a β attitude Manganse Dioxide through X-ray powder diffraction, and TEM testing product pattern is an one-dimensional rod-like.
Claims (5)
1, a kind of synthetic method of nano material of manganese dioxide, it is characterized in that in being dissolved with the soluble salt solution of bivalent manganese, add superoxol, stir, insert then in the reactor, heating reaction down finishes, and is cooled to room temperature then, through washing and dry, get taraxacum shape nano material of manganese dioxide again.
2, a kind of synthetic method of nano material of manganese dioxide, it is characterized in that in being dissolved with the soluble salt solution of bivalent manganese, add superoxol, stir, slowly add the weakly alkaline aqueous solution then, post precipitation to be generated is inserted in the reactor, heating reaction down finishes, be cooled to room temperature again, after washing and dry gets bar-shaped nano material of manganese dioxide.
3, the synthetic method of nano material of manganese dioxide according to claim 2 is characterized in that the preferred ammoniacal liquor of described weak base, Tri N-Propyl Amine, n-Butyl Amine 99, hexamethylenetetramine.
4, the synthetic method of nano material of manganese dioxide according to claim 1 and 2 is characterized in that the described preferred manganous nitrate of soluble salt solution of bivalent manganese, the aqueous solution of manganous sulfate of being dissolved with.
5, the synthetic method of nano material of manganese dioxide according to claim 1 and 2 is characterized in that described temperature of reaction is 150-260 ℃, and the reaction times is 3-15 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100432044A CN1308245C (en) | 2005-03-30 | 2005-03-30 | Method for synthesizing nano material of manganese dioxide in dandelion and stick shape |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100432044A CN1308245C (en) | 2005-03-30 | 2005-03-30 | Method for synthesizing nano material of manganese dioxide in dandelion and stick shape |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1686826A true CN1686826A (en) | 2005-10-26 |
| CN1308245C CN1308245C (en) | 2007-04-04 |
Family
ID=35304868
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100432044A Expired - Fee Related CN1308245C (en) | 2005-03-30 | 2005-03-30 | Method for synthesizing nano material of manganese dioxide in dandelion and stick shape |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1308245C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101372363B (en) * | 2008-09-26 | 2011-07-20 | 中国科学院电工研究所 | Synthetic alpha-MnO 2 Method for micron hollow sphere and nanocluster |
| WO2012083511A1 (en) * | 2010-12-20 | 2012-06-28 | 海洋王照明科技股份有限公司 | Preparation method and use of manganese dioxide nano-rod |
| CN106807364A (en) * | 2017-03-31 | 2017-06-09 | 厦门大学 | A kind of wet oxidizing catalyst and preparation method thereof |
| CN111470540A (en) * | 2020-03-18 | 2020-07-31 | 北京化工大学 | Method for inducing oxygen vacancy content in metal oxide to be improved by complexation effect |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0611650B2 (en) * | 1985-08-02 | 1994-02-16 | 中央電気工業株式会社 | Manganese dioxide production method |
| JP3146359B2 (en) * | 1999-08-04 | 2001-03-12 | 工業技術院長 | Ultrafine manganese oxide powder and method for producing the same |
| CN100457637C (en) * | 2002-12-24 | 2009-02-04 | 上海大学 | Method for preparing nano manganese dioxide |
-
2005
- 2005-03-30 CN CNB2005100432044A patent/CN1308245C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101372363B (en) * | 2008-09-26 | 2011-07-20 | 中国科学院电工研究所 | Synthetic alpha-MnO 2 Method for micron hollow sphere and nanocluster |
| WO2012083511A1 (en) * | 2010-12-20 | 2012-06-28 | 海洋王照明科技股份有限公司 | Preparation method and use of manganese dioxide nano-rod |
| CN103153870A (en) * | 2010-12-20 | 2013-06-12 | 海洋王照明科技股份有限公司 | Preparation method and use of manganese dioxide nano-rod |
| JP2014504252A (en) * | 2010-12-20 | 2014-02-20 | ▲海▼洋王照明科技股▲ふん▼有限公司 | Manufacturing method and application of manganese dioxide nanorods |
| CN103153870B (en) * | 2010-12-20 | 2015-04-15 | 海洋王照明科技股份有限公司 | Preparation method and use of manganese dioxide nano-rod |
| CN106807364A (en) * | 2017-03-31 | 2017-06-09 | 厦门大学 | A kind of wet oxidizing catalyst and preparation method thereof |
| CN106807364B (en) * | 2017-03-31 | 2019-08-06 | 厦门大学 | A kind of wet oxidizing catalyst and preparation method thereof |
| CN111470540A (en) * | 2020-03-18 | 2020-07-31 | 北京化工大学 | Method for inducing oxygen vacancy content in metal oxide to be improved by complexation effect |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1308245C (en) | 2007-04-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Low-temperature conversion synthesis of M (OH) 2 (M= Ni, Co, Fe) nanoflakes and nanorods | |
| CN1673094A (en) | Synthesis process of nano zinc oxide material | |
| Kobayashi et al. | Hydrothermal synthesis of brookite-type titanium dioxide with snowflake-like nanostructures using a water-soluble citratoperoxotitanate complex | |
| CN102502783B (en) | Method for preparing alkali zinc chloride nano-powder in hexagonal flake structures | |
| CN102082270A (en) | Manganese spinel nano material as well as preparation method and application of manganese spinel nano material | |
| CN109908915B (en) | Magnetic visible-light-driven photocatalyst for treating hexavalent chromium wastewater and preparation method thereof | |
| CN110745784B (en) | Metal oxide nano-particles and preparation method and application thereof | |
| CN101857260A (en) | Method for preparing spherical cerium dioxide nano material with square-sheet surface structure by hydrothermal method | |
| CN101618895A (en) | Multi-level structure alpha type nickel hydroxide prepared by microwave auxiliary and method thereof | |
| CN1308245C (en) | Method for synthesizing nano material of manganese dioxide in dandelion and stick shape | |
| CN106115798B (en) | A kind of MnCo2O4Hexagonal nanometer rods and method for preparing Nano cube | |
| CN103170646A (en) | Synthetic method of nanometer materials of cobalt fractal structure | |
| CN1644282A (en) | Production for nanometer nickel powder | |
| Xing et al. | Hydrothermal-assisted homogeneous precipitation synthesis of dumbbell-like MnCO3 nanostructures | |
| CN111675238A (en) | Method for preparing multi-morphology nano zinc oxide by solid phase method | |
| CN105271443B (en) | Method for preparing flaky nano CoO or Co3O4 through assistant microwave heating | |
| CN106517360A (en) | Particle self-assembly type micro-spherical tricobalt tetroxide powder and preparation method thereof | |
| CN1285509C (en) | Method for preparing unidimensional Al00H and gamma-Al2O3 nano materials | |
| CN102134103A (en) | Method for preparing hydroxyl iron oxide nanowire | |
| CN100486901C (en) | Synthesis method of cobaltosic oxide nano-tube | |
| CN102328960B (en) | Synthesis method of trimanganese tetroxide material with 3D (three-dimensional) flower-shaped structure | |
| CN113184823B (en) | Method for preparing cobalt nickel phosphate microsphere material | |
| CN1073482C (en) | Method for producing superfine sphere metallic nickel powder | |
| CN108946796A (en) | A kind of doped titanate and preparation method thereof | |
| CN100425539C (en) | Synthesis method of nickel hydroxide nano-tube |
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 | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |