CN101219809B - Process for producing mangano-manganic oxide nanocrystalline with controllable sizing and shape - Google Patents
Process for producing mangano-manganic oxide nanocrystalline with controllable sizing and shape Download PDFInfo
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- CN101219809B CN101219809B CN2007101935389A CN200710193538A CN101219809B CN 101219809 B CN101219809 B CN 101219809B CN 2007101935389 A CN2007101935389 A CN 2007101935389A CN 200710193538 A CN200710193538 A CN 200710193538A CN 101219809 B CN101219809 B CN 101219809B
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Abstract
The invention provides a method for preparing manganic manganous oxide nano-crystalline with controllable size and shape. aThe manganes source and organic coating agent are put into toluene to be heated and dissolved; water solution added alkaline matter is reacted for 10 minutes to 240 hours under a temperature ranging from 25 DEG C to 280 DEG C; the reaction is carried out under an atmospheric pressure or in an autoclave; under a heating condition, the manganese source is hydrolyzed; through the process of formation and growth of crystal nucleus, the manganic manganous oxide nano-crystallinecoated by the organic ligand is formed finally. The method for preparing the total material of the invention is characterized by moderate reaction condition, simple and easy operation and short prepa ring period, thus, the preparation is easy to be enlarged. The prepared manganic manganous oxide nano-particle can disperse in non-polar organic solution. By regulating reaction time, reaction temperature, alkali amount, water amount and type of the organic coating agent, spherical, square and polygonal manganic manganous oxide nano-crystalline coated by the organic ligand of different sizes (3-50nm) can be compounded.
Description
Technical field
The invention belongs to and utilize two phase process to prepare the synthetic method of mangano-manganic oxide nanocrystalline, relate to the synthetic method of the controlled mangano-manganic oxide nanocrystalline of size and dimension in conjunction with autoclave.
Background technology
Mn
3O
4Have many uses, on electronic industry, it is a raw material of producing soft magnetic ferrite, soft magnetic ferrite then is widely used as magnetic recording material; On chemical industry, it can be used as multiple catalyst for reaction.In addition, Mn
3O
4Also can be used as the colorant of some paint or coating, contain Mn
3O
4Paint or paint spay-coating on iron and steel, have better corrosion resistance than paint that contains titanium dioxide or ferric oxide or coating.In addition, Mn
3O
4Also can be used as the positive electrode active materials spinel LiMn of preparation battery
2O
4Precursor etc.Mn
3O
4Small-size effect, quantum effect, surface effects, interfacial effect and the macro quanta tunnel effect of interior ground rice body because of having nanocrystal will show than body phase material excellent magnetism energy and catalytic activity more.Mn
3O
4The traditional preparation process method 2 kinds of roasting method and reduction methods are arranged.In recent years, adopt liquid phase method to prepare Mn
3O
4As sol-gel method or coprecipitation method (chemical material 1997,9,750.Chem.Mater.1997,9,750.) but the product that obtains still need just can be transformed into Mn through high-temperature calcination
3O
4(the material communication 1995,25,127 of water method.Mater.Lett.1995,25,127.) synthetic Mn
3O
4Nanoparticle can not be dispersed in certain solvent well, and the size of particle is bigger.General resulting particle is in micro-meter scale and wider distribution.Pyrolysated method (chemical material 2004,16,3931.Chem.Mater.2004; 16,3931.) require temperature higher, greatly about about 300 ℃, and the particle shape of preparation is more single, be sphere substantially.
Summary of the invention
Temperature of reaction height, restive nanocrystalline size and dimension and the nanocrystalline shortcoming that is difficult to be dispersed in the organic solvent of institute's synthetic when synthesizing in order to solve traditional single phase.The synthetic method that the purpose of this invention is to provide a kind of mangano-manganic oxide nanocrystalline of organic ligand coating is that institute's synthetic trimanganese tetroxide nano size of particles and shape are all controlled, and distribution of sizes is narrower with the preparation method of two phase process in conjunction with autoclave.Investigate from angle of practical application, its magnetic performance difference of the mangano-manganic oxide nanocrystalline of different size, shape is used more extensive.Therefore, the hot method of two-phase institute synthetic size, controllable shapes, and the mangano-manganic oxide nanocrystalline that can be dissolved in the organic solvent can be widely used in the production of reality and life.
The step of method of the present invention and condition are:
The manganese source of adopting is: dodecyl sodium sulfonate manganese, lauric acid manganese, manganese stearate or manganese oleate;
Organic coating is: amino dodecane, oleyl amine, cetylamine, oleic acid, trioctyl-phosphine oxide, ten alkyl carboxylic acids, dodecyl carboxylic acid, tetradecyl carboxylic acid, hexadecyl carboxylic acid or octadecyl carboxylic acid or positive hot carboxylic acid;
Alkaline matter is: ammonium hydroxide, Trimethylamine, triethylamine, tripropylamine, TERTIARY BUTYL AMINE, urea, sodium-acetate, Potassium ethanoate, Sulfothiorine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetra isopropyl ammonium hydroxide, TBAH, trimethylamine oxide, oxidation triethylamine, oxidation tripropyl amine, oxidation Tributylamine, sodium hydroxide or potassium hydroxide;
The mol ratio of manganese source and alkaline matter was from 10: 1 to 1: 10; The mol ratio in organic coating and manganese source is 1000: 1 to 1: 10.
According to raw-material proportioning, manganese source and organic coating are joined heating for dissolving in the toluene, add the aqueous solution of alkaline matter, under 25-280 ℃ of condition, react 10min-240h, be reflected under the normal pressure and carry out; Perhaps carry out in the autoclave, pressure is at 1MPa-10MPa, and manganese source hydrolysis under the condition of 90-280 ℃ of heating forms and process of growth through nucleus, obtains mangano-manganic oxide nanocrystalline at last; The described nanocrystalline 3-50nm that is of a size of is shaped as square, sphere or Polygons.
The whole preparation methods of the present invention has the reaction conditions gentleness, the characteristics that method is simple, and preparation cycle is short, thereby be easy to amplify preparation.Prepared trimanganese tetroxide nano particle can be dispersed in the non-polar organic solvent.The type of the amount of the alkali by adjusting reaction time, temperature of reaction, reaction, the amount of water and organic coating can be synthesized the mangano-manganic oxide nanocrystalline that spherical, square, the polygonal organic ligand of different size (3-50nm) coats.
Description of drawings
Fig. 1 is the trimanganese tetroxide electromicroscopic photograph that obtains under the differential responses temperature.Among the figure, (a) being 120 ℃ of trimanganese tetroxide electromicroscopic photographs, (d) is 150 ℃ of trimanganese tetroxide electromicroscopic photographs, and 150 ℃ (g) is 180 ℃ of trimanganese tetroxide electromicroscopic photographs; (b, c120 ℃, (e, f) 150 ℃ and (h, i) 180 ℃ are respectively electron diffraction and high-resolution electron microscopy photo accordingly.
Embodiment
Embodiment 1: the preparation of the mangano-manganic oxide nanocrystalline that spherical (3nm) organic ligand coats
62 milligrams of manganese stearates, 1.0ml oleyl amine and 5ml toluene are joined the teflon lined of the autoclave of 30ml, the aqueous solution that again 15ml is contained the 0.4ml TERTIARY BUTYL AMINE adds system, autoclave is sealed and put into the inherent 180 ℃ of heating 4h (pressure remains on 1-10MPa) of stove, the cooling back generates at the spherical mangano-manganic oxide nanocrystalline that oil phase has brown organic ligand to coat.Its particle diameter is about 3nm.
Embodiment 2: the preparation of square (15nm) mangano-manganic oxide nanocrystalline
62 milligrams of TETRADECONIC ACID manganese, 0.5ml oleic acid and 10ml toluene are joined the teflon lined of the autoclave of 30ml, the aqueous solution that again 10ml is contained the 0.10ml Tributylamine adds system, autoclave is sealed and put into the inherent 120 ℃ of heating 2h of stove, (pressure remains on 1-10MPa) cooling back generates at the square shape mangano-manganic oxide nanocrystalline that oil phase has brown organic ligand to coat.Its particle diameter is about 15nm.
Embodiment 3: the preparation of square (9nm) mangano-manganic oxide nanocrystalline
The teflon lined internal heating of autoclave that 62 milligrams of manganese oleates, 0.5g stearic acid and 5ml toluene is joined 30ml is to water white transparency, behind cool to room temperature, the aqueous solution that again 15.0ml is contained the 0.4ml TERTIARY BUTYL AMINE adds system, autoclave is sealed and put into the inherent 100 ℃ of heating 8h (pressure remains on 1-10MPa) of stove, the cooling back generates at the square shape mangano-manganic oxide nanocrystalline that oil phase has brown organic ligand to coat.Its particle diameter is about 9nm.
Embodiment 4: the preparation of Polygons (10nm) mangano-manganic oxide nanocrystalline
The teflon lined internal heating of autoclave that 186 milligrams of dodecyl sodium sulfonate manganese, 1.0g trioctyl phosphine oxide and 5ml toluene is joined 30ml is to water white transparency, behind cool to room temperature, the aqueous solution that again 20ml is contained the 0.1ml trimethylamine oxide adds system, autoclave is sealed and put into the inherent 240 ℃ of heating 12h (pressure remains on 1-10MPa) of stove, the cooling back generates at the polygonal mangano-manganic oxide nanocrystalline that oil phase has brown organic ligand to coat.Its particle diameter is about 10nm.
Embodiment 5: the preparation of square (13nm) mangano-manganic oxide nanocrystalline
The teflon lined internal heating of autoclave that 0.62 gram lauric acid manganese, 1.0g dodecyl carboxylic acid and 10ml toluene is joined 30ml is to water white transparency, behind cool to room temperature, the aqueous solution that again 2ml is contained 0.24g urea adds system, autoclave is sealed and put into the inherent 100 ℃ of heating 8h (pressure remains on 1-10MPa) of stove, the cooling back generates at the square shape mangano-manganic oxide nanocrystalline that oil phase has brown organic ligand to coat.Its particle diameter is about 13nm.
Embodiment 6: the preparation of spherical (20nm) mangano-manganic oxide nanocrystalline
The teflon lined internal heating of autoclave that 0.31 gram manganese oleate, 1.0g amino dodecane and 5ml toluene is joined 30ml is to water white transparency, behind cool to room temperature, the aqueous solution that again 30ml is contained the 0.5g sodium-acetate adds system, autoclave is sealed and put into the inherent 180 ℃ of heating 144h (pressure remains on 1-10MPa) of stove, the cooling back generates at the spherical mangano-manganic oxide nanocrystalline that oil phase just has brown organic ligand to coat.Its particle diameter is about 20nm.
Embodiment 7: the preparation of spherical (50nm) mangano-manganic oxide nanocrystalline
0.15 gram lauric acid manganese, 0.5g cetylamine and 10ml toluene are joined 100 ℃ of the there-necked flask internal heating of 100ml to water white transparency, the aqueous solution that under agitation 10ml is contained the 0.8ml triethylamine joins in the flask rapidly, at 100 ℃ of heating 2h, the cooling back generates at the spherical mangano-manganic oxide nanocrystalline that oil phase has brown organic ligand to coat.Its particle diameter is about 50nm.
Embodiment 8: the preparation of spherical (15nm) mangano-manganic oxide nanocrystalline
62 milligrams of manganese stearates, 0.5g TETRADECONIC ACID and 10ml toluene are joined 100 ℃ of the there-necked flask internal heating of 100ml to water white transparency, the aqueous solution that under agitation 2ml is contained 0.4ml oxidation Tributylamine joins in the flask rapidly, at 60 ℃ of heating 4h, the cooling back generates at the spherical mangano-manganic oxide nanocrystalline that oil phase has brown organic ligand to coat.Its particle diameter is about 15nm.
Claims (3)
1. the preparation method of the controlled mangano-manganic oxide nanocrystalline of size and dimension is characterized in that its step and condition are:
The manganese source of adopting is: dodecyl sodium sulfonate manganese, lauric acid manganese, manganese stearate or manganese oleate;
Organic coating is: amino dodecane, oleyl amine, cetylamine, oleic acid, trioctyl-phosphine oxide, ten alkyl carboxylic acids, dodecyl carboxylic acid, tetradecyl carboxylic acid, hexadecyl carboxylic acid or octadecyl carboxylic acid or positive hot carboxylic acid;
Alkaline matter is: ammonium hydroxide, Trimethylamine, triethylamine, tripropylamine, TERTIARY BUTYL AMINE, urea, sodium-acetate, Potassium ethanoate, Sulfothiorine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetra isopropyl ammonium hydroxide, TBAH, trimethylamine oxide, oxidation triethylamine, oxidation tripropyl amine, oxidation Tributylamine, sodium hydroxide or potassium hydroxide;
The mol ratio of manganese source and alkaline matter was from 10: 1 to 1: 10; The mol ratio in organic coating and manganese source is 1000: 1 to 1: 10;
According to raw-material proportioning, manganese source and organic coating are joined heating for dissolving in the toluene, add the aqueous solution of alkaline matter, under 60-100 ℃ of condition, react 10min-240h, be reflected under the normal pressure and carry out; Perhaps carry out in the autoclave, pressure is at 1MPa-10MPa, and manganese source hydrolysis under the condition of 90-280 ℃ of heating forms and process of growth through nucleus, obtains mangano-manganic oxide nanocrystalline at last.
2. the preparation method of the mangano-manganic oxide nanocrystalline that size and dimension as claimed in claim 1 is controlled is characterized in that described mangano-manganic oxide nanocrystalline is of a size of 3-50nm, is shaped as sphere or Polygons.
3. the preparation method of the mangano-manganic oxide nanocrystalline that size and dimension as claimed in claim 2 is controlled is characterized in that described Polygons is square.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102040246B (en) * | 2010-10-27 | 2013-04-24 | 江苏科技大学 | Method for synthesizing manganous-manganic oxide nano material at room temperature by using mild path |
| CN102328960B (en) * | 2011-09-02 | 2013-04-03 | 上海大学 | Synthesis method of trimanganese tetroxide material with 3D (three-dimensional) flower-shaped structure |
| CN102730762B (en) * | 2012-06-26 | 2014-08-27 | 深圳市新昊青科技有限公司 | Low BET ball-type manganic manganous oxide and its preparation method |
| CN102701285B (en) * | 2012-06-26 | 2014-08-27 | 贵州红星发展股份有限公司 | Methods for preparing low specific surface area (BET) manganous manganic oxide and controlling granularity and manganous manganic oxide |
| CN103787419B (en) * | 2014-01-23 | 2015-08-26 | 复旦大学 | A kind of preparation method of trimanganese tetroxide nano particulate material |
| CN114057237B (en) * | 2021-11-05 | 2022-08-26 | 广东佳纳能源科技有限公司 | Composite ternary precursor and preparation method and application thereof |
Citations (3)
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|---|---|---|---|---|
| EP0107275A1 (en) * | 1982-09-30 | 1984-05-02 | Chemetals Incorporated | Preparation of Mn3O4 |
| JP2815611B2 (en) * | 1989-05-10 | 1998-10-27 | 正同化学工業株式会社 | Method for producing manganese oxide |
| CN1295978A (en) * | 2000-12-25 | 2001-05-23 | 化学工业部天津化工研究设计院 | Process for preparing manganor manganic oxide used for soft magnetic ferrite |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0107275A1 (en) * | 1982-09-30 | 1984-05-02 | Chemetals Incorporated | Preparation of Mn3O4 |
| JP2815611B2 (en) * | 1989-05-10 | 1998-10-27 | 正同化学工業株式会社 | Method for producing manganese oxide |
| CN1295978A (en) * | 2000-12-25 | 2001-05-23 | 化学工业部天津化工研究设计院 | Process for preparing manganor manganic oxide used for soft magnetic ferrite |
Non-Patent Citations (5)
| Title |
|---|
| Zhang Weixin et al.Low temperature synthesis of nanocrystalline Mn3O4 by asolvothermal method.Solid State Ionics117.1999,117331-335. * |
| 汤林等.水热法四氧化三锰超细粉体的研制与表征.矿冶工程23 2.2003,23(2),63-65. |
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| 潘其经.四氧化三锰的制备方法与发展前景.中国锰业16 3.1998,16(3),51-55. |
| 潘其经.四氧化三锰的制备方法与发展前景.中国锰业16 3.1998,16(3),51-55. * |
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Effective date of registration: 20230727 Address after: No. 5625 Renmin Avenue, Chaoyang District, Changchun City, Jilin Province, 130012 Patentee after: CHANGCHUN INSTITUTE OF APPLIED CHEMISTRY CHINESE ACADEMY OF SCIENCES Address before: No. 9, river Hai Dong Road, Changzhou, Jiangsu Province Patentee before: CHANGZHOU INSTITUTE OF ENERGY STORAGE MATERIALS & DEVICES |