CN101597085A - Mesoporous manganese oxide nano granule and preparation method thereof - Google Patents
Mesoporous manganese oxide nano granule and preparation method thereof Download PDFInfo
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- CN101597085A CN101597085A CNA200910069719XA CN200910069719A CN101597085A CN 101597085 A CN101597085 A CN 101597085A CN A200910069719X A CNA200910069719X A CN A200910069719XA CN 200910069719 A CN200910069719 A CN 200910069719A CN 101597085 A CN101597085 A CN 101597085A
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Abstract
The present invention relates to a kind of mesoporous manganese oxide nano material and preparation method thereof; by the hydrothermal of manganese metal and manganese acetate and ammoniacal liquor and the control of roasting subsequently; preparation has the mesoporous and grain diameter of the uniform distribution of aperture 2～10 nanometers controlled hydroxide oxygen manganese and mixture, eight oxidations, five manganese single crystal particles or manganic oxide single crystal particle of trimanganese tetroxide in 20～80 nanometer range, and combustion reactions plays katalysis to toluene for they.Preparation method of the present invention is simple, and synthesis condition is loose, easily repeat, and raw material is cheap, can carry out scale operation.
Description
Technical field
The present invention relates to a kind of mesoporous manganese oxide nano material and preparation method thereof, belong to inorganic porous material and field of nanometer material technology.
Background technology
Manganese oxide is a kind of important chemical material, is widely used in the reduction of organic pollutant and electrode materials etc.At present existing document is made vesicular structure and nano particle with manganese oxide, in the hope of improving its catalytic activity and chemical property.Paper publishing adopts the surfactant templates method to prepare mesoporous manganese oxide at Science 276 (1997) 926 and Chem.Commun. (1997) 1031, but the particle of gained material is usually at micron order and irregular, and used tensio-active agent need be removed in synthetic back in synthetic, and operating process is loaded down with trivial details.Chinese patent CN1467159A discloses a kind of porous manganese oxide nano flake material, and with the potassium permanganate and the long chain alkyl ammonium salt reaction gained of equimolar amount, pore size distribution is big (4-50nm).Chinese patent CN1513767A discloses a kind of preparation method of ultra-fine Manganse Dioxide, prepares in the tensio-active agent microemulsion system, and the gained sample particle is less, but does not have mesoporous property.Chinese patent CN1438181A discloses a kind of preparation method of nano-manganese dioxide, is raw material with potassium permanganate, and the alkyl alcohol Soxylat A 25-7 is reductive agent and surface dispersant, and the manganese oxide particle of preparation does not have mesoporous property yet.We adopt a kind of easy method, synthesize under surfactant-free exists to have the mesoporous manganese oxide nano granule of uniform distribution, and its thing can obtain β-MnOOH and Mn by controlling different maturing temperatures mutually
3O
4Mixture, Mn
5O
8Single crystal particle, and Mn
2O
3Single crystal particle, combustion reactions plays katalysis to toluene for they.
Summary of the invention
The object of the present invention is to provide a kind of mesoporous manganese oxide nano granule material and preparation method thereof, can overcome the shortcoming of prior art.Synthesis device of the present invention is simple, and is easy to operate, and condition is loose, the energy is saved in less contamination, and raw material is simple and easy to, and is with low cost, and output is big, and crystalline structure is controlled.
In order to achieve the above object, the present invention adopts the method for the hydrothermal treatment consists of manganese metal and manganese acetate and ammonia soln, the preparation mesoporous manganese oxide nano granule.Experimental technique can obtain the mesoporous manganese oxide of different size by regulating the ratio of manganese metal and manganese acetate, and particle size also can regulate simultaneously, and the crystallization phases of manganese oxide can be controlled by roasting.The preparation process of this material comprises following two kinds of schemes:
Method A:a) a certain amount of manganese acetate is dissolved in the ammonia soln, stirring at normal temperature adds Sodium Fluoride and water after 30～60 minutes, restir is after 2 hours, and mixture is transferred in the stainless steel cauldron that contains poly-tetrafluoro inner bag, add the manganese sheet then, 170～180 ℃ of hydrothermal treatment consists 24 hours; B) after the cooling, filtration, washing, 80 ℃ of dryings obtain brown ceramic powder, again roasting at a certain temperature;
Or method B:a) a certain amount of manganese powder and manganese acetate are mixed be dissolved in the ammonia soln, normal temperature stirred down after 30～60 minutes, and mixture is transferred in the stainless steel cauldron that contains poly-tetrafluoro inner bag, 170～180 ℃ of hydrothermal treatment consists 24 hours; B) after the cooling, filtration, washing, 80 ℃ of dryings obtain brown ceramic powder, again roasting at a certain temperature.
The mol ratio of described manganese acetate and manganese sheet or manganese powder is 1～1.2, and the ammonia concn of use is 25%, and the mol ratio of ammoniacal liquor and manganese is 50～100.
Described maturing temperature is 80～800 ℃, and roasting time 1～4 hour need not protection of inert gas.
The synthetic brown ceramic powder sample that obtains is the mixture of hydroxide oxygen manganese and trimanganese tetroxide, can obtain the mesoporous manganese oxide nano granule of different crystalline phases and different pore sizes under differing temps after the roasting.
The synthetic brown ceramic powder sample that obtains obtains eight oxidations, five manganese nanometer monocrystalline particles 400 ℃ of following roastings after 3～4 hours, obtain manganic oxide nanometer monocrystalline particle after 3～4 hours 700 ℃ of following roastings.
Combustion reactions plays katalysis to described mesoporous manganese oxide nano granule to toluene.
The present invention has following characteristics:
1. adopting cheap, nontoxic manganese acetate and manganese powder or manganese sheet is reactant, does not use any tensio-active agent or template, helps environment protection.
2. can be by regulating the mesoporous manganese oxide nano crystal particles that different manganese source ratio and temperature of reaction obtain granular size scope 20-80 nanometer and aperture 2-10 nanometer.
3. preparation technology and equipment are simple, controllable oxidization manganese grain diameter, mesoporous distribution and crystal phase structure.
4. Zhi Bei material has good toluene combustion catalysis performance, has industrial application value.
Embodiment
Embodiment 1:
3.4 gram manganese acetates are dissolved in 10ml 25% ammonia soln, stir half an hour at normal temperatures after, add 5ml water and 0.2gNaF, this moment, the pH value of solution value was about 13.Continue to stir after 2 hours, mixture is transferred in the stainless steel cauldron that contains poly-tetrafluoro inner bag, simultaneously 3g manganese sheet is put into system, 180 ℃ of hydrothermal treatment consists 24 hours, then after filtration, clean, obtain the brown solid powder after 80 ℃ of dryings.The material that the XRD test shows makes is β-MnOOH and Mn
3O
4The mixture phase; SEM shows that grain diameter is about 20～50nm; The TEM display material has irregular mesoporous; Nitrogen adsorption isotherm and graph of pore diameter distribution show that this material has typical meso-hole structure, and its BET specific surface area is 15m
2/ g; Mesoporous aperture is 3nm.
Embodiment 2:
With heat-up rate in retort furnace the roasting of embodiment 1 preparation sample with 2 ℃/min, roasting stopped after 3 hours after 400 ℃, and XRD spectra shows that the gained material is Mn
5O
8Single crystal particle, SEM show that grain diameter is about 20～80nm; The TEM display material has irregular mesoporous; Nitrogen adsorption-desorption isotherm and corresponding graph of pore diameter distribution thereof show that this material has typical meso-hole structure, and the BET specific surface area is 10m
2/ g, mesoporous aperture is 6nm.
Embodiment 3:
Will be according to of heat-up rate in retort furnace the roasting of embodiment 1 preparation sample with 2 ℃/min, roasting stopped after 3 hours after 700 ℃, and the XRD spectra display material of gained material is Mn
2O
3Single crystal particle, SEM show that grain diameter is about 20～80nm, and the TEM display material has irregular mesoporous; Nitrogen adsorption-desorption isotherm and corresponding graph of pore diameter distribution thereof show that this material has typical meso-hole structure, and the BET specific surface area is 8m
2/ g, mesoporous aperture is 10nm.
Embodiment 4:
0.55 gram manganese powder is mixed in the ammonia soln that is dissolved in 10ml 25% with 2.45 gram manganese acetates, and vigorous stirring is 30～60 minutes at normal temperatures.The mol ratio of mixed solution is 1Mn: 1Mn (CH
3COOH)
2: 100NH
3H
2O.Then mixed solution is transferred in the stainless steel cauldron that contains poly-tetrafluoro inner bag 170 ℃ of hydrothermal treatment consists 24 hours.To collect the brown solid powder after sample filtering, washing, 80 ℃ of dried overnight after the cooling.The XRD test result shows that the gained powdered sample is β-MnOOH (JCPDS#18-0804) and Mn
3O
4(JCPDS#80-0382) mixture phase; The SEM photo shows that the grain diameter of the material that obtains is about 45nm; The TEM display material has irregular mesoporous; Nitrogen adsorption-desorption isotherm and corresponding graph of pore diameter distribution thereof show that this material has typical meso-hole structure, and the BET specific surface area is 33m
2/ g, mesoporous aperture is 2nm.
Embodiment 5:
With the heat-up rate roasting in retort furnace with 2 ℃/min of the sample of embodiment 4 preparation, roasting is 3 hours after 400 ℃.The sample structure that obtains is Mn
5O
8(JCPDS 39-1218, C2/m, a=1.034nm, b=0.572nm, c=0.485nm, β=109.4 °), grain diameter is about 20～80nm, and the BET specific surface area is 15m
2/ g, mesoporous aperture is 4.2nm.
Embodiment 6:
With the heat-up rate roasting in retort furnace with 2 ℃/min of the sample of embodiment 4 preparation, roasting is 3 hours after 700 ℃.The sample structure that obtains is Mn
2O
3(a=0.9414nm), grain diameter is about 20～80nm for JCPDS 71-0636, Ia-3, and the BET specific surface area is 10m
2/ g; Mesoporous aperture is 6.3m.
Claims (4)
1, a kind of mesoporous manganese oxide nano granule material, it is characterized in that it has the equally distributed mesoporous of aperture 2～10 nanometers, grain diameter is controlled in 20～80 nanometer range, is the mixture of hydroxide oxygen manganese and trimanganese tetroxide, eight oxidations, five manganese single crystal particles, the manganic oxide single crystal particle.
2, a kind of method for preparing the described mesoporous manganese oxide nano granule of claim 1, it is characterized in that it comprises the steps: method A:a) a certain amount of manganese acetate is dissolved in the ammonia soln, stirring at normal temperature adds Sodium Fluoride and water after 30～60 minutes, behind the restir 2 hours, mixture is transferred in the stainless steel cauldron that contains poly-tetrafluoro inner bag, add the manganese sheet then, 170～180 ℃ of hydrothermal treatment consists 24 hours; B) after the cooling, filtration, washing, 80 ℃ of dryings obtain brown ceramic powder, again roasting at a certain temperature;
Or method B:a) a certain amount of manganese powder and manganese acetate are mixed be dissolved in the ammonia soln, normal temperature stirred down after 30～60 minutes, and mixture is transferred in the stainless steel cauldron that contains poly-tetrafluoro inner bag, 170～180 ℃ of hydrothermal treatment consists 24 hours; B) after the cooling, filtration, washing, 80 ℃ of dryings obtain brown ceramic powder, again roasting at a certain temperature.
3, the preparation method of a kind of mesoporous manganese oxide nano granule according to claim 2 is characterized in that, the mol ratio of described manganese acetate and manganese sheet or manganese powder is 0.8～1.2, and the ammonia concn of use is 25%, and the mol ratio of ammoniacal liquor and manganese is 50～100.
4, the preparation method of a kind of mesoporous manganese oxide nano granule according to claim 2 is characterized in that, maturing temperature is 80～800 ℃, and roasting time 1～4 hour need not protection of inert gas.
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|---|---|---|---|---|
| CN102259928A (en) * | 2011-05-20 | 2011-11-30 | 浙江大学 | Method for preparing Mn3O4 nano-particles |
| CN102285689A (en) * | 2011-07-06 | 2011-12-21 | 河北工业大学 | Preparation method of gamma-phase nano manganese oxide material |
| CN102557143A (en) * | 2010-12-07 | 2012-07-11 | 海洋王照明科技股份有限公司 | Preparation method of Mn2O3 and catalyst |
| CN102867655A (en) * | 2012-10-16 | 2013-01-09 | 桂林电子科技大学 | Tubular mesoporous manganese dioxide supercapacitor and preparation method thereof |
| CN103717536A (en) * | 2011-06-02 | 2014-04-09 | 康奈尔大学 | Manganese oxide nanoparticles, method and application |
| CN103740210A (en) * | 2014-01-26 | 2014-04-23 | 南通广泰生化制品有限公司 | Microporous type nano coating |
| CN103769579A (en) * | 2014-01-26 | 2014-05-07 | 江苏鹰球集团有限公司 | Method for preparing carbon-encapsulated Cu/Mn2O composite porous material |
| CN105858732A (en) * | 2016-06-01 | 2016-08-17 | 中国工程物理研究院化工材料研究所 | Manganese sesquioxide nano structure regulation method and manganese sesquioxide powder |
| CN105883925A (en) * | 2016-06-25 | 2016-08-24 | 上海大学 | Mesoporous trimanganese tetraoxide and preparation method thereof |
| CN106158431A (en) * | 2016-09-18 | 2016-11-23 | 北京化工大学 | A kind of preparation method and application of basic oxide nano-array super capacitor material |
| CN113690453A (en) * | 2020-05-18 | 2021-11-23 | 中国科学院上海硅酸盐研究所 | Mn (manganese)5O8Nano cage-shaped oxygen reduction electrocatalyst and preparation method thereof |
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2009
- 2009-07-14 CN CN200910069719XA patent/CN101597085B/en not_active Expired - Fee Related
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557143A (en) * | 2010-12-07 | 2012-07-11 | 海洋王照明科技股份有限公司 | Preparation method of Mn2O3 and catalyst |
| CN102557143B (en) * | 2010-12-07 | 2015-03-18 | 海洋王照明科技股份有限公司 | Preparation method of Mn2O3 and catalyst |
| CN102259928B (en) * | 2011-05-20 | 2013-02-20 | 浙江大学 | Method for preparing Mn3O4 nano-particles |
| CN102259928A (en) * | 2011-05-20 | 2011-11-30 | 浙江大学 | Method for preparing Mn3O4 nano-particles |
| CN103717536A (en) * | 2011-06-02 | 2014-04-09 | 康奈尔大学 | Manganese oxide nanoparticles, method and application |
| CN103717536B (en) * | 2011-06-02 | 2017-02-15 | 康奈尔大学 | Manganese oxide nanoparticles, method and application |
| CN102285689A (en) * | 2011-07-06 | 2011-12-21 | 河北工业大学 | Preparation method of gamma-phase nano manganese oxide material |
| CN102867655B (en) * | 2012-10-16 | 2015-08-05 | 桂林电子科技大学 | Ultracapacitor of tubulose meso-porous titanium dioxide manganese and preparation method thereof |
| CN102867655A (en) * | 2012-10-16 | 2013-01-09 | 桂林电子科技大学 | Tubular mesoporous manganese dioxide supercapacitor and preparation method thereof |
| CN103740210A (en) * | 2014-01-26 | 2014-04-23 | 南通广泰生化制品有限公司 | Microporous type nano coating |
| CN103740210B (en) * | 2014-01-26 | 2016-03-23 | 南通广泰生化制品有限公司 | A kind of microporous nano coating |
| CN103769579B (en) * | 2014-01-26 | 2016-05-25 | 江苏鹰球集团有限公司 | The preparation method of the coated Cu/Mn2O composite porous material of a kind of carbon |
| CN103769579A (en) * | 2014-01-26 | 2014-05-07 | 江苏鹰球集团有限公司 | Method for preparing carbon-encapsulated Cu/Mn2O composite porous material |
| CN105858732A (en) * | 2016-06-01 | 2016-08-17 | 中国工程物理研究院化工材料研究所 | Manganese sesquioxide nano structure regulation method and manganese sesquioxide powder |
| CN105883925A (en) * | 2016-06-25 | 2016-08-24 | 上海大学 | Mesoporous trimanganese tetraoxide and preparation method thereof |
| CN106158431A (en) * | 2016-09-18 | 2016-11-23 | 北京化工大学 | A kind of preparation method and application of basic oxide nano-array super capacitor material |
| CN113690453A (en) * | 2020-05-18 | 2021-11-23 | 中国科学院上海硅酸盐研究所 | Mn (manganese)5O8Nano cage-shaped oxygen reduction electrocatalyst and preparation method thereof |
| CN113690453B (en) * | 2020-05-18 | 2022-08-09 | 中国科学院上海硅酸盐研究所 | Mn (manganese) 5 O 8 Nano cage-shaped oxygen reduction electrocatalyst and preparation method thereof |
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