CN1308245C - 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
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- CN1308245C CN1308245C CNB2005100432044A CN200510043204A CN1308245C CN 1308245 C CN1308245 C CN 1308245C CN B2005100432044 A CNB2005100432044 A CN B2005100432044A CN 200510043204 A CN200510043204 A CN 200510043204A CN 1308245 C CN1308245 C CN 1308245C
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Abstract
The present invention provides a method for synthesizing a taraxacum-shaped manganese dioxide nanometer material and a rod-shaped manganese dioxide nanometer material. The method for synthesizing the taraxacum-shaped manganese dioxide nanometer material comprises: a hydrogen peroxide solution is added into a soluble salt solution dissolved with divalent manganese to be put into a reaction vessel after being stirred, and the reaction is ended under the heating condition; then the hydrogen peroxide solution and the soluble salt solution are cooled to the room temperature, and the taraxacum-shaped manganese dioxide nanometer material can be formed by the processes of washing and drying. The method for synthesizing the rod-shaped manganese dioxide nanometer material mainly comprises: the hydrogen peroxide solution is added into the soluble salt solution dissolved with the divalent manganese to be stirred; then a weakly alkaline water solution is slowly added and is put into the reaction vessel until settlements are generated, the reaction is ended under the heating condition, the hydrogen peroxide solution and the soluble salt solution are cooled to the room temperature, and the rod-shaped manganese dioxide nanometer material can be formed finally by the processes of washing and drying.
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.Henry, N.Baffier, 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 methodes such as Sugantha have prepared α-MnO in the presence of template
2Nanometer rod [M.Sugantha, P.A.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 8ml 30% 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 13ml 3mol/L manganous sulfate, add 5ml 30% 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 2ml 30% 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 5ml 0.5mol/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 12ml 0.5mol/L manganous sulfate, add 2ml 30% 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 5ml 0.5mol/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 (4)
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, reacted 3-15 hour down, be cooled to room temperature again in 150-260 ℃, after washing and dry, taraxacum shape nano material of manganese dioxide.
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, reacted 3-15 hour down in 150-260 ℃, be cooled to room temperature again, after washing and dry gets bar-shaped nano material of manganese dioxide.
3, the synthetic method of bar-shaped nano material of manganese dioxide according to claim 2 is characterized in that described weak base is selected from ammoniacal liquor, Tri N-Propyl Amine, n-Butyl Amine 99 or hexamethylenetetramine.
4, the synthetic method of nano material of manganese dioxide according to claim 1 and 2 is characterized in that the described soluble salt solution that is dissolved with bivalent manganese is selected from the aqueous solution of manganous nitrate or manganous sulfate.
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| CNB2005100432044A CN1308245C (en) | 2005-03-30 | 2005-03-30 | Method for synthesizing nano material of manganese dioxide in dandelion and stick shape |
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| CNB2005100432044A CN1308245C (en) | 2005-03-30 | 2005-03-30 | Method for synthesizing nano material of manganese dioxide in dandelion and stick shape |
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| CN1308245C true CN1308245C (en) | 2007-04-04 |
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Families Citing this family (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 |
| EP2657191A4 (en) * | 2010-12-20 | 2017-04-12 | Ocean's King Lighting Science & Technology Co., Ltd. | Preparation method and use of manganese dioxide nano-rod |
| CN106807364B (en) * | 2017-03-31 | 2019-08-06 | 厦门大学 | A kind of wet oxidizing catalyst and preparation method thereof |
| CN111470540B (en) * | 2020-03-18 | 2021-06-22 | 北京化工大学 | Method for inducing oxygen vacancy content in metal oxide to be improved by complexation effect |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6230622A (en) * | 1985-08-02 | 1987-02-09 | Chuo Denki Kogyo Kk | Production of manganese dioxide |
| JP2001048546A (en) * | 1999-08-04 | 2001-02-20 | Agency Of Ind Science & Technol | Ultramicroparticulate manganese oxide powder and its production |
| CN1438181A (en) * | 2002-12-24 | 2003-08-27 | 上海大学 | Method for preparing nano manganese dioxide |
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2005
- 2005-03-30 CN CNB2005100432044A patent/CN1308245C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6230622A (en) * | 1985-08-02 | 1987-02-09 | Chuo Denki Kogyo Kk | Production of manganese dioxide |
| JP2001048546A (en) * | 1999-08-04 | 2001-02-20 | Agency Of Ind Science & Technol | Ultramicroparticulate manganese oxide powder and its production |
| CN1438181A (en) * | 2002-12-24 | 2003-08-27 | 上海大学 | Method for preparing nano manganese dioxide |
Non-Patent Citations (4)
| Title |
|---|
| MN02纳米晶的水热合成及表征 李亚栋，李成韦，李龙泉，钱逸泰，高等学校化学学报，第18卷第9期 1997 * |
| MN02纳米棒的循环伏安行为研究 袁中直，周震涛，李伟等，精细化工，第21卷第2期 2004 * |
| MN02纳米棒的循环伏安行为研究 袁中直，周震涛，李伟等，精细化工，第21卷第2期 2004;MN02纳米晶的水热合成及表征 李亚栋，李成韦，李龙泉，钱逸泰，高等学校化学学报，第18卷第9期 1997;不同形状MN02超微粒子的制备 李亚栋，李成韦，钱逸泰，刘元辉，李龙泉，应用化学，第14卷第2期 1997 * |
| 不同形状MN02超微粒子的制备 李亚栋，李成韦，钱逸泰，刘元辉，李龙泉，应用化学，第14卷第2期 1997 * |
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