CN102583559A - Preparation method of nanometer alpha-manganese dioxide (MnO2) hollow ball - Google Patents
Preparation method of nanometer alpha-manganese dioxide (MnO2) hollow ball Download PDFInfo
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- CN102583559A CN102583559A CN2011100014710A CN201110001471A CN102583559A CN 102583559 A CN102583559 A CN 102583559A CN 2011100014710 A CN2011100014710 A CN 2011100014710A CN 201110001471 A CN201110001471 A CN 201110001471A CN 102583559 A CN102583559 A CN 102583559A
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Abstract
The invention discloses a preparation method of a nanometer alpha-manganese dioxide (MnO2) hollow ball, which comprises the following steps that: bivalent soluble manganese salt and potassium peroxydisulfate solution with given concentrations are respectively prepared, and the bivalent soluble manganese salt is selected from one of manganous sulfate, manganese chloride and manganese acetate; the solution is blended inside a reaction vessel according to an equivalent mol ratio, the temperature is controlled between 20 DEG C and 90 DEG C, the mixed solution is insulated and held for 1 to 96 hours, and products are filtered, washed and dried to obtain a product of the nanometer alpha-MnO2 hollow ball. The preparation method is carried out in normal-pressure low-temperature liquid, so a pressure-resistant vessel is not required, no surface active agent or other additives are added, no blending is required, the reaction is moderate, simplicity in operation is realized, and the cost is low.
Description
Technical field
The invention belongs to a kind of manganese bioxide material preparation method, particularly a kind of nano grade alpha-MnO
2The preparation method of hollow ball.
Background technology
Manganse Dioxide is cheap with it, and environmental friendliness becomes a kind of important starting material in the energy and the electronic applications, is widely used in fields such as alkaline Mn cell, ferromagnetic substance.The Manganse Dioxide of discovering nanometer in recent years is as unique with excellent performance is arranged in molecular sieve and the catalyzer in ultracapacitor and lithium ion battery and the chemical industry.The physicochemical property of Manganse Dioxide depend on pattern, crystalline structure, volume to a great extent; Parameters such as density; Therefore, the nano material of manganese dioxide of preparation different crystal forms and different-shape becomes research focus in recent years, the micron order manganese dioxide hollow sphere of especially being made up of nanofiber.
The compound method method of manganese dioxide hollow sphere template commonly used and hydrothermal method.Application number is in 200610086152.3 the Chinese patent " W/O emulsion template legal system is equipped with the method for nano-manganese dioxide microballoon ", is that raw material is being prepared the nano-manganese dioxide microballoon that particle diameter is 80-250nm through the W/O emulsion template technology that the organic liquids such as normal hexane that add tensio-active agent form under the magnetic agitation and under 20-80 ℃ with Sodium Metabisulfite and potassium permanganate.This method is used a large amount of organic solvent and tensio-active agent, and the preparation process is complicated.Application number is Chinese invention patent " a kind of synthetic α-MnO of 200810223039.4
2The method of micrometre hollow sphere and nanometer team bunch " in, be that raw material reacts 1-12h under 110-140 ℃ hydrothermal condition with Potassium Persulphate and manganous sulfate and the vitriol oil, prepare α-MnO
2Micrometre hollow sphere can generate α-MnO through adding aluminum nitrate
2Star-like nanometer team bunch.Application number is that 201010187852.8 Chinese invention patent is that raw material reacts 12-46h under 140-160 ℃ of hydrothermal condition with potassium permanganate, N-butyl-pyridinium a tetrafluoro borate, hydrochloric acid, synthesizes the Manganse Dioxide of hollow polyhedral pattern.Application number is that 200910023579.2 Chinese invention patent synthesizes manganese dioxide hollow sphere with potassium permanganate, manganous sulfate and soluble ferric iron salt under hydrothermal condition.The used hydrothermal method of aforesaid method need be carried out under higher pressure and temperature, and the resistance to pressure of equipment has been proposed high requirement, also need add chemical substances such as sulfuric acid, organic solvent and additive in the system in addition.People such as Xie Yi are with AgNO
3For catalyzer has prepared α-MnO with Potassium Persulphate oxidation manganous sulfate under normal pressure
2Tiny balloon (Z.Q.Li, Y.Ding, Y.J.Xiong, Q.Yang and Y.Xie, Chem.Commun., 2005,918), but this method reactant concn is low excessively, long reaction time, and used expensive Silver Nitrate as catalyzer.
Summary of the invention
The present invention is directed to the problem of aforesaid method, proposed a kind of preparation nano grade alpha-MnO
2The method of hollow ball.This method can generate spherical α-MnO under the atmospheric pressure at room condition
2Particulate, this spherical particle is fibrous by manganese dioxide nano, and diameter is between 2～10 μ m, and inside is hollow structure.The technical scheme that the present invention adopts is: a kind of nano grade alpha-MnO
2The preparation method of hollow ball is characterized in that: include following operation:
1. dispose certain density divalence soluble manganese salt and potassium persulfate solution respectively; Above-mentioned solution such as is pressed at mol ratio in reaction vessel, mix, temperature is controlled between 20--90 ℃, insulation 1--96h; Product can obtain product of the present invention through filtration, deionized water wash and drying.
2. a kind of nano grade alpha-MnO according to claim 1
2The preparation method of hollow ball is characterized in that: the divalence soluble manganese salt described in the claim 1 is selected from a kind of of manganous sulfate, Manganous chloride tetrahydrate and manganese acetate, and the concentration of its solution is 0.01-3.0mol.L
-1, preferred 0.05-1.5mol.L
-1
3. a kind of nano grade alpha-MnO according to claim 1
2The preparation method of hollow ball is characterized in that: its concentration of the potassium persulfate solution described in the claim 1 is 0.01-2.0mol.L
-1, preferred 0.05-1.5mol.L
-1
4. a kind of nano grade alpha-MnO according to claim 1
2The preparation method of hollow ball is characterized in that: the drying temperature described in the claim 1 is 60-120 ℃, and drying time is 5-24h.
5. a kind of nano grade alpha-MnO according to claim 1
2The preparation method of hollow ball is characterized in that: reaction vessel at insulating process for not adding any stirring or disturbance.
6. a kind of nano grade alpha-MnO according to claim 1
2The preparation method of hollow ball is characterized in that: the preferred 40-60 of holding temperature ℃, and the preferred 2-10h of soaking time.
Technology of the present invention need not adopt the HTHP hydrothermal reactor; Also not adding any tensio-active agent and other additive, is that raw material generates the nano grade alpha-MnO that is made up of nanofiber under normal pressure, low temperature and immobilized liquid phase environment with the solubility manganous salt and the Potassium Persulphate of cheapness
2Hollow ball, its microballoon size can be through temperature of reaction and time control.
Description of drawings
Fig. 1 is the SEM photo of instance 1 synthetic Manganse Dioxide of the present invention
Fig. 2 is the single hollow ball SEM of instance 1 a synthetic Manganse Dioxide of the present invention photo
Fig. 3 is the SEM photo after instance 1 synthetic Manganse Dioxide of the present invention grinds fragmentation
Fig. 4 is instance 1 a synthetic Manganse Dioxide XRD figure spectrum of the present invention
Embodiment:
In conjunction with following instance the present invention is elaborated
Instance 1
Prepare 0.1mol.L respectively
-1Each 100ml of manganese sulfate solution and potassium persulfate solution places the 500ml reaction vessel; Reaction vessel is placed thermostat container; Temperature is controlled at 50 ℃ of static 10h of insulation; Till the sedimentation and filtration that generates, deionized water wash to filtrating detected to go out adularescent and precipitate with barium chloride solution, filter cake placed 80 ℃ of baking ovens to dry 10h, can obtain MnO
2Tiny balloon, this microballoon size is 4-6 μ m, detects through the X-powdery diffractometry to be α-MnO
2Crystalline structure.
Instance 2
Prepare 0.1mol.L respectively
-1Each 100ml of manganese sulfate solution and potassium persulfate solution places the 500ml reaction vessel; Reaction vessel is placed thermostat container; Temperature is controlled at 50 ℃ of static 5h of insulation; Till the sedimentation and filtration that generates, deionized water wash to filtrating detected to go out adularescent and precipitate with barium chloride solution, filter cake placed 80 ℃ of baking ovens to dry 10h, can obtain MnO
2Tiny balloon, this microballoon size is 2-4 μ m, detects through the X-powdery diffractometry to be α-MnO
2Crystalline structure.
Instance 3
Prepare 0.1mol.L respectively
-1Each 100ml of manganese sulfate solution and potassium persulfate solution places the 500ml reaction vessel; Reaction vessel is placed thermostat container; Temperature is controlled at 50 ℃ of static 15h of insulation; Till the sedimentation and filtration that generates, deionized water wash to filtrating detected to go out adularescent and precipitate with barium chloride solution, filter cake placed 80 ℃ of baking ovens to dry 10h, can obtain MnO
2Tiny balloon, this microballoon size is 5-8 μ m, detects through the X-powdery diffractometry to be α-MnO
2Crystalline structure.
Instance 4
Prepare 0.5mol.L respectively
-1Each 100ml of manganese chloride solution and potassium persulfate solution places the 500ml reaction vessel; The static 72h of insulation under room temperature (25-30 ℃) environment; Till the sedimentation and filtration that generates, deionized water wash to filtrating detect to go out adularescent and precipitate with barium chloride solution; Filter cake places 100 ℃ of baking ovens to dry 8h, can obtain α-MnO
2Tiny balloon, the microballoon size is 4-6 μ m
Instance 5
Prepare 0.5mol.L respectively
-1Manganese acetate solution 100ml and 1.0mol.L
-1Potassium persulfate solution 50ml places the 500ml reaction vessel, and at 80 ℃ of static 2h of insulation, the sedimentation and filtration of generation, deionized water wash are till detects to go out white precipitate with barium chloride solution, and filter cake places 120 ℃ of baking ovens to dry 5 hours, can obtain α-MnO
2Tiny balloon, the microballoon size is 3-5 μ m.
Instance 6
Prepare 1mol.L respectively
-1Manganese sulfate solution and 1mol.L
-1Each 150ml of potassium persulfate solution places the 500ml reaction vessel; At 60 ℃ of static 2h of insulation; The sedimentation and filtration that generates, deionized water wash to filtrating detect to go out till the white precipitate with barium chloride solution, and filter cake places 100 ℃ of baking ovens to dry 10 hours, can obtain α-MnO
2Tiny balloon, the microballoon size is 2-4 μ m.
Claims (6)
1. nano grade alpha-MnO
2The preparation method of hollow ball is characterized in that: include following operation:
Dispose certain density divalence soluble manganese salt and potassium persulfate solution respectively; Above-mentioned solution such as is pressed at mol ratio in reaction vessel, mix, temperature is controlled between 20--90 ℃, insulation 1--96h; Product can obtain product of the present invention through filtration, deionized water wash and drying.
2. a kind of nano grade alpha-MnO according to claim 1
2The preparation method of hollow ball is characterized in that: the divalence soluble manganese salt described in the claim 1 is selected from a kind of of manganous sulfate, Manganous chloride tetrahydrate and manganese acetate, and the concentration of its solution is 0.01-3.0mol.L
-1, preferred 0.05-1.5mol.L
-1
3. a kind of nano grade alpha-MnO according to claim 1
2The preparation method of hollow ball is characterized in that: its concentration of the potassium persulfate solution described in the claim 1 is 0.01-2.0mol.L
-1, preferred 0.05-1.5mol.L
-1
4. a kind of nano grade alpha-MnO according to claim 1
2The preparation method of hollow ball is characterized in that: the drying temperature described in the claim 1 is 60-120 ℃, and drying time is 5-24h.
5. a kind of nano grade alpha-MnO according to claim 1
2The preparation method of hollow ball is characterized in that: reaction vessel at insulating process for not adding any stirring or disturbance.
6. a kind of nano grade alpha-MnO according to claim 1
2The preparation method of hollow ball is characterized in that: the preferred 40-60 of holding temperature ℃, and the preferred 2-10h of soaking time.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591290A (en) * | 2013-10-31 | 2015-05-06 | 无锡华臻新能源科技有限公司 | Preparation method for hollow spherical manganese dioxide for supercapacitors |
| CN107555481A (en) * | 2016-11-18 | 2018-01-09 | 虔东稀土集团股份有限公司 | A kind of Mn oxide material and preparation method thereof |
| CN107986335A (en) * | 2017-12-14 | 2018-05-04 | 上海第二工业大学 | A kind of method that manganese dioxide particle is prepared using waste and old ternary dynamic lithium battery positive electrode |
| WO2019033695A1 (en) * | 2017-08-12 | 2019-02-21 | 虔东稀土集团股份有限公司 | Manganese oxide material and method for preparing same |
| CN110104689A (en) * | 2019-03-27 | 2019-08-09 | 河南省人民医院 | A kind of hollow manganese dioxide nano particle and preparation method thereof |
| CN112010400A (en) * | 2020-07-20 | 2020-12-01 | 西安怡速安智能科技有限公司 | Anode layer formula of electrochemical electrode for water sterilization |
| CN113371759A (en) * | 2021-08-13 | 2021-09-10 | 河南师范大学 | Preparation method and application of amorphous transition metal oxide packaged manganese-based oxide composite material |
| CN113716612A (en) * | 2021-05-11 | 2021-11-30 | 山东精工电子科技有限公司 | Synthesis method of manganese dioxide hollow sphere structure |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101372363A (en) * | 2008-09-26 | 2009-02-25 | 中国科学院电工研究所 | Synthetic alpha-MnO 2 Method for micron hollow sphere and nanocluster |
| CN101624213A (en) * | 2009-08-13 | 2010-01-13 | 陕西师范大学 | Preparation method for manganese dioxide hollow sphere |
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2011
- 2011-01-06 CN CN2011100014710A patent/CN102583559A/en active Pending
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| CN101372363A (en) * | 2008-09-26 | 2009-02-25 | 中国科学院电工研究所 | Synthetic alpha-MnO 2 Method for micron hollow sphere and nanocluster |
| CN101624213A (en) * | 2009-08-13 | 2010-01-13 | 陕西师范大学 | Preparation method for manganese dioxide hollow sphere |
Non-Patent Citations (1)
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| HONG-EN WANG, ET AL.: "Facile synthesis and electrochemical characterization of hierarchical α-MnO2 spheres", 《JOURNAL OF ALLOYS COMPOUNDS》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591290A (en) * | 2013-10-31 | 2015-05-06 | 无锡华臻新能源科技有限公司 | Preparation method for hollow spherical manganese dioxide for supercapacitors |
| CN107555481A (en) * | 2016-11-18 | 2018-01-09 | 虔东稀土集团股份有限公司 | A kind of Mn oxide material and preparation method thereof |
| CN107555481B (en) * | 2016-11-18 | 2024-01-09 | 虔东稀土集团股份有限公司 | Manganese oxide material and preparation method thereof |
| WO2019033695A1 (en) * | 2017-08-12 | 2019-02-21 | 虔东稀土集团股份有限公司 | Manganese oxide material and method for preparing same |
| CN107986335A (en) * | 2017-12-14 | 2018-05-04 | 上海第二工业大学 | A kind of method that manganese dioxide particle is prepared using waste and old ternary dynamic lithium battery positive electrode |
| CN110104689A (en) * | 2019-03-27 | 2019-08-09 | 河南省人民医院 | A kind of hollow manganese dioxide nano particle and preparation method thereof |
| CN110104689B (en) * | 2019-03-27 | 2021-08-13 | 河南省人民医院 | Hollow manganese dioxide nano-particles and preparation method thereof |
| CN112010400A (en) * | 2020-07-20 | 2020-12-01 | 西安怡速安智能科技有限公司 | Anode layer formula of electrochemical electrode for water sterilization |
| CN113716612A (en) * | 2021-05-11 | 2021-11-30 | 山东精工电子科技有限公司 | Synthesis method of manganese dioxide hollow sphere structure |
| CN113371759A (en) * | 2021-08-13 | 2021-09-10 | 河南师范大学 | Preparation method and application of amorphous transition metal oxide packaged manganese-based oxide composite material |
| CN113371759B (en) * | 2021-08-13 | 2021-10-29 | 河南师范大学 | Preparation method and application of amorphous transition metal oxide packaged manganese-based oxide composite material |
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Application publication date: 20120718 |