CN101844814B - Preparation method of hollow manganese dioxide polyhedron - Google Patents
Preparation method of hollow manganese dioxide polyhedron Download PDFInfo
- Publication number
- CN101844814B CN101844814B CN2010101878528A CN201010187852A CN101844814B CN 101844814 B CN101844814 B CN 101844814B CN 2010101878528 A CN2010101878528 A CN 2010101878528A CN 201010187852 A CN201010187852 A CN 201010187852A CN 101844814 B CN101844814 B CN 101844814B
- Authority
- CN
- China
- Prior art keywords
- manganese dioxide
- preparation
- hollow manganese
- deionized water
- hours
- 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.)
- Expired - Fee Related
Links
Images
Abstract
The invention relates to a preparation method of a hollow manganese dioxide polyhedron, comprising the following steps of: adding 1 part of potassium permanganate, 0-0.16 part of N-butylpyridinetetrafluoroborate, 185 parts of deionized water and 4.5-7.2 parts of hydrochloric acid in a molar ratio; adding the potassium permanganate and the N-butyl pyridinetetrafluoroborate into the deionized water;sufficiently stirring until solids are dissolved; then adding 36 weight percent of hydrochloric acid; evenly stirring; transferring the obtained solution to a hydro-thermal reaction kettle; carrying out hydro-thermal reaction in the water at the constant temperature of 140-160 DEG C for 12-46 hours; naturally cooling to the room temperature; washing the product for 3 times with the deionized water; putting the solids in a 50 DEG C drying oven and drying for 6 hours to prepare the hollow manganese dioxide polyhedron. The method has mild reaction condition, simple processing steps and low production cost, and the prepared hollow manganese dioxide polyhedron has regular morphology and even particle size distribution which is 3-5mu m respectively.
Description
Technical field
The invention belongs to the material technology field, be specifically related to hollow manganese dioxide polyhedron material.
Background technology
Manganse Dioxide is as a kind of important inorganic functional material, and physics that it is special and chemical property make this type of material show wide application prospect in fields such as catalysis, ion-exchange, selective adsorption, biosensor, lithium-ion secondary cell and ultracapacitors.Result of study finds that the different-shape manganese bioxide material has been showed very big difference in nature, thereby the controlled preparation and the property research work thereof of different-shape Manganse Dioxide has been subjected to great attention.In recent years, the research work that ionic liquid is used for controlled preparation different-shape inorganic functional material got more and more, but carried out different-shape manganese oxide material preparation work report seldom with ionic liquid as soft template.
Compare with traditional tensio-active agent, ionic liquid at room temperature has low-steam pressure, good thermostability, good character such as wide electrochemical window and selective dissolution ability are strong.Over past ten years, ionic liquid has obtained widely using in field of inorganic material preparing technology, particularly has field such as ionic liquid material to obtain progress in the micro Nano material of metal nano material, non-metallic element material, silicon-dioxide, metal organosilicon, metal oxide, metallic sulfide, metal-salt, open skeleton structure, material that ionic liquid is modified and load.Ionic liquid has unique pattern for preparation, and the controlled inorganic functional material of crystalline phase provides new opportunity.
Summary of the invention
The technical problem to be solved in the present invention is to provide that a kind of method is simple, pattern is regular, the uniform preparation method of hollow manganese dioxide polyhedron of size distribution.
Solving the problems of the technologies described above the technical scheme that is adopted is that it is made up of following step:
1, preparation hollow manganese dioxide polyhedron
Mol ratio with potassium permanganate, N-butyl-pyridinium a tetrafluoro borate, deionized water and hydrochloric acid is 1: 0.078～0.16: 185: 4.5～7.2, potassium permanganate, N-butyl-pyridinium a tetrafluoro borate are joined in the deionized water, be stirred well to the solid dissolving, add massfraction again and be 36% hydrochloric acid, stir, gained solution is transferred in the hydrothermal reaction kettle, 140～160 ℃ of thermostat(t)ed water thermal responses 12～46 hours, naturally cools to room temperature.
2, drying
With product deionized water wash 3 times that step 1 obtains, solid placed 50 ℃ of baking ovens dry 6 hours, prepared the hollow manganese dioxide polyhedron.
In the hollow manganese dioxide polyhedron step 1 of the present invention's preparation, the optimum mole ratio of potassium permanganate and N-butyl-pyridinium a tetrafluoro borate, deionized water and hydrochloric acid is 1: 0.13: 185: 6.
In the hollow manganese dioxide polyhedron step 1 of the present invention preparation, best hydrothermal temperature is that 150 ℃, time are 36 hours.
The present invention utilizes hydrothermal method that potassium permanganate and hydrochloric acid are reacted under the condition that with ionic liquid N-butyl-pyridinium a tetrafluoro borate is soft template, be prepared into pattern rule, the uniform hollow manganese dioxide polyhedron of size distribution, this method reaction conditions gentleness, processing step is simple, production cost is low.
Description of drawings
Fig. 1 is the polyhedral X ray diffracting spectrum of hollow manganese dioxide of the embodiment of the invention 1 preparation.
Fig. 2 is the polyhedral infrared spectra curve of hollow manganese dioxide of the embodiment of the invention 1 preparation.
Fig. 3 is the polyhedral thermogravimetric curve of hollow manganese dioxide of the embodiment of the invention 1 preparation.
Fig. 4 is the polyhedral stereoscan photograph of hollow manganese dioxide of the embodiment of the invention 1 preparation.
Fig. 5 is that the hydrochloric acid consumption is the Manganse Dioxide stereoscan photograph of 0mL preparation.
Fig. 6 is that the hydrochloric acid consumption is the Manganse Dioxide stereoscan photograph of 0.5mL preparation.
Fig. 7 is that the hydrochloric acid consumption is the Manganse Dioxide stereoscan photograph of 1.0mL preparation.
Fig. 8 is that the hydrochloric acid consumption is the polyhedral stereoscan photograph of hollow manganese dioxide of 1.5mL preparation.
Fig. 9 is that the hydrochloric acid consumption is the polyhedral stereoscan photograph of hollow manganese dioxide of 2.1mL preparation.
Figure 10 is that the hydrochloric acid consumption is the polyhedral stereoscan photograph of hollow manganese dioxide of 2.2mL preparation.
Figure 11 is that the hydrochloric acid consumption is the polyhedral stereoscan photograph of hollow manganese dioxide of 2.3mL preparation.
Figure 12 is that the hydrochloric acid consumption is the polyhedral stereoscan photograph of hollow manganese dioxide of 2.4mL preparation.
Figure 13 is that N-butyl-pyridinium a tetrafluoro borate consumption is the polyhedral stereoscan photograph of hollow manganese dioxide of 0g preparation.
Figure 14 is that N-butyl-pyridinium a tetrafluoro borate consumption is the polyhedral stereoscan photograph of hollow manganese dioxide of 0.0223g preparation.
Figure 15 is that N-butyl-pyridinium a tetrafluoro borate consumption is the polyhedral stereoscan photograph of hollow manganese dioxide of 0.0669g preparation.
Figure 16 is that N-butyl-pyridinium a tetrafluoro borate consumption is the polyhedral stereoscan photograph of hollow manganese dioxide of 0.1204g preparation.
Figure 17 is that N-butyl-pyridinium a tetrafluoro borate consumption is the polyhedral stereoscan photograph of hollow manganese dioxide of 0.1248g preparation.
Figure 18 is that N-butyl-pyridinium a tetrafluoro borate consumption is the polyhedral stereoscan photograph of hollow manganese dioxide of 0.1382g preparation.
Figure 19 is the stereoscan photograph of the Manganse Dioxide of hydro-thermal reaction preparation in 1 hour.
Figure 20 is the stereoscan photograph of the Manganse Dioxide of hydro-thermal reaction preparation in 2 hours.
Figure 21 is the stereoscan photograph of the Manganse Dioxide of hydro-thermal reaction preparation in 3 hours.
Figure 22 is the solid polyhedral stereoscan photograph of Manganse Dioxide of hydro-thermal reaction preparation in 6 hours.
Figure 23 is the polyhedral stereoscan photograph of hollow manganese dioxide of hydro-thermal reaction preparation in 12 hours.
Figure 24 is the polyhedral stereoscan photograph of hollow manganese dioxide of hydro-thermal reaction preparation in 24 hours.
Figure 25 is the polyhedral stereoscan photograph of hollow manganese dioxide of hydro-thermal reaction preparation in 38 hours.
Figure 26 is the polyhedral stereoscan photograph of hollow manganese dioxide of hydro-thermal reaction preparation in 40 hours.
Figure 27 is the polyhedral stereoscan photograph of hollow manganese dioxide of hydro-thermal reaction preparation in 42 hours.
Figure 28 is the polyhedral stereoscan photograph of hollow manganese dioxide of hydro-thermal reaction preparation in 46 hours.
Figure 29 is the stereoscan photograph of the Manganse Dioxide of hydro-thermal reaction preparation in 48 hours.
Figure 30 is the stereoscan photograph of the Manganse Dioxide of hydro-thermal reaction preparation in 60 hours.
Figure 31 is that hydrothermal temperature is the stereoscan photograph of the Manganse Dioxide of 100 ℃ of preparations.
Figure 32 is that hydrothermal temperature is the stereoscan photograph of the Manganse Dioxide of 120 ℃ of preparations.
Figure 33 is that hydrothermal temperature is the polyhedral stereoscan photograph of hollow manganese dioxide of 140 ℃ of preparations.
Figure 34 is that hydrothermal temperature is the polyhedral stereoscan photograph of hollow manganese dioxide of 160 ℃ of preparations.
Embodiment
The present invention is described in more detail below in conjunction with drawings and Examples, but the invention is not restricted to these embodiment.
1, preparation hollow manganese dioxide polyhedron
Mol ratio with potassium permanganate, N-butyl-pyridinium a tetrafluoro borate, deionized water and hydrochloric acid is 1: 0.13: 185: 6,0.6320g potassium permanganate, 0.1115g N-butyl-pyridinium a tetrafluoro borate are joined in the 13mL deionized water, be stirred well to the solid dissolving, add the 2mL massfraction again and be 36% hydrochloric acid, stir, gained solution is transferred in the 25mL hydrothermal reaction kettle, 150 ℃ of thermostat(t)ed water thermal responses 36 hours, naturally cools to room temperature.
2, drying
With product deionized water wash 3 times that step 1 obtains, solid placed 50 ℃ of baking ovens dry 6 hours, was prepared into the hollow manganese dioxide polyhedron.
Prepared hollow manganese dioxide polyhedron characterizes with Rigaku D/Max2550VB+/PC type X-ray diffractometer, EQUINX type Fourier transformation infrared spectrometer, Q1000DSC+LNCS+FACS Q600SDT type thermal analyzer, Quanta 200 type scanning electronic microscope, and characterization result is seen Fig. 1～4.As seen from Figure 1, prepared hollow manganese dioxide polyhedron is a β type Manganse Dioxide.As seen from Figure 2, product is at 523cm
-1, 656cm
-1The place shows the charateristic avsorption band of manganese oxygen key.In Fig. 3, TGA is the thermogravimetric curve of product, and DSC is the product differential scanning calorimetric curve, and as seen from Figure 3, the weight-loss curve ownership at 667 ℃ and 973 ℃ two places is converted into more stable manganese and oxygen compound for Manganse Dioxide.As seen from Figure 4, prepared Manganse Dioxide size distribution is even, is hollow polyhedral.
Embodiment 2
Mol ratio with potassium permanganate, N-butyl-pyridinium a tetrafluoro borate, deionized water and hydrochloric acid is 1: 0: 185: 4.5,0.6320g potassium permanganate, 0gN-butyl-pyridinium a tetrafluoro borate are joined in the 13mL deionized water, be stirred well to the solid dissolving, add the 1.5mL massfraction again and be 36% hydrochloric acid, stir, gained solution is transferred in the 25mL hydrothermal reaction kettle, 150 ℃ of thermostat(t)ed water thermal responses 36 hours, naturally cools to room temperature.Other steps are identical with embodiment 1, are prepared into the hollow manganese dioxide polyhedron.
Mol ratio with potassium permanganate, N-butyl-pyridinium a tetrafluoro borate, deionized water and hydrochloric acid is 1: 0.026: 185: 4.5,0.6320g potassium permanganate, 0.0223g N-butyl-pyridinium a tetrafluoro borate are joined in the 13mL deionized water, be stirred well to the solid dissolving, add the 1.5mL massfraction again and be 36% hydrochloric acid, stir, gained solution is transferred in the 25mL hydrothermal reaction kettle, 150 ℃ of thermostat(t)ed water thermal responses 36 hours, naturally cools to room temperature.Other steps are identical with embodiment 1, are prepared into the hollow manganese dioxide polyhedron.
Embodiment 4
Mol ratio with potassium permanganate, N-butyl-pyridinium a tetrafluoro borate, deionized water and hydrochloric acid is 1: 0.16: 185: 7.2,0.6320g potassium permanganate, 0.1382gN-butyl-pyridinium a tetrafluoro borate are joined in the 13mL deionized water, be stirred well to the solid dissolving, add the 2.4mL massfraction again and be 36% hydrochloric acid, stir, gained solution is transferred in the 25mL hydrothermal reaction kettle, 150 ℃ of thermostat(t)ed water thermal responses 36 hours, naturally cools to room temperature.Other steps are identical with embodiment 1, are prepared into the hollow manganese dioxide polyhedron.
Mol ratio with potassium permanganate, N-butyl-pyridinium a tetrafluoro borate, deionized water and hydrochloric acid is 1: 0.078: 185: 6.6,0.6320g potassium permanganate, 0.0669g N-butyl-pyridinium a tetrafluoro borate are joined in the 13mL deionized water, be stirred well to the solid dissolving, add the 2.2mL massfraction again and be 36% hydrochloric acid, stir, gained solution is transferred in the 25mL hydrothermal reaction kettle, 150 ℃ of thermostat(t)ed water thermal responses 36 hours, naturally cools to room temperature.Other steps are identical with embodiment 1, are prepared into the hollow manganese dioxide polyhedron.
Embodiment 6
In embodiment 1～5 preparation hollow manganese dioxide polyhedron step 1,140 ℃ of thermostat(t)ed water thermal responses 46 hours naturally cool to room temperature, and other steps of this step are identical with corresponding embodiment.Other steps are identical with embodiment 1, are prepared into the hollow manganese dioxide polyhedron.
In embodiment 1～5 preparation hollow manganese dioxide polyhedron step 1,160 ℃ of thermostat(t)ed water thermal responses 12 hours, naturally cool to room temperature, other steps of this step are identical with corresponding embodiment.Other steps are identical with embodiment 1, are prepared into the hollow manganese dioxide polyhedron.
In order to determine optimised process step of the present invention, the contriver has carried out a large amount of laboratory study tests, and various test situation are as follows:
Laboratory apparatus: homogeneous reactor, model are KLJX-12, are produced by upright robot institute of high and new technology industrial development zone, Yantai section; X-ray diffractometer, model are Rigaku D/Max2550VB+/PC, are produced by Japan company of science; Scanning electronic microscope, model are Quanta 200, are produced by FEI Co.; Fourier transformation infrared spectrometer, model are EQUINX, are produced by German Brucher company; Thermo System (model is Q1000DSC+LNCS+FACS Q600SDT, is produced by U.S. TA company) is measured water in products content.
1, the add-on of hydrochloric acid is to the influence of Manganse Dioxide pattern
With potassium permanganate, N-butyl-pyridinium a tetrafluoro borate, the mol ratio of deionized water and hydrochloric acid was respectively 1: 0.13: 185: 0,1: 0.13: 185: 1.5,1: 0.13: 185: 3,1: 0.13: 185: 4.5,1: 0.13: 185: 6,1: 0.13: 185: 6.3,1: 0.13: 185: 6.6,1: 0.13: 185: 6.9,1: 0.13: 185: 7.2, with 0.6320g potassium permanganate and 0.1115g N-butyl-pyridinium a tetrafluoro borate totally 9 parts join respectively in the 13mL deionized water, be stirred well to the solid dissolving, add 0mL more respectively successively, 0.5mL, 1.0mL, 1.5mL, 2mL, 2.1mL, 2.2mL, 2.3mL, 2.4mL massfraction is 36% hydrochloric acid, stir, gained solution is transferred in the 25mL hydrothermal reaction kettle, 150 ℃ of thermostat(t)ed water thermal responses 36 hours, naturally cool to room temperature, product deionized water wash 3 times placed 50 ℃ of baking ovens dry 6 hours.
By Fig. 4～12 as seen, when the add-on of hydrochloric acid was respectively 0mL, 0.5mL and 1.0mL, the Manganse Dioxide pattern of preparation was irregular; When the add-on of hydrochloric acid is respectively 1.5mL, 2.0mL, 2.1mL, 2.2mL, 2.3mL, 2.4mL, the Manganse Dioxide of preparation all has similar hollow polyhedral pattern, size is distributed in 3～5 mu m ranges, when wherein the add-on of hydrochloric acid is 2.0mL, homogeneity and size of particles the best of prepared hollow manganese dioxide polyhedron pattern.
2, the add-on of N-butyl-pyridinium a tetrafluoro borate is to the influence of Manganse Dioxide pattern
With potassium permanganate, N-butyl-pyridinium a tetrafluoro borate, the mol ratio of deionized water and hydrochloric acid was respectively 1: 0: 185: 6,1: 0.026: 185: 6,1: 0.078: 185: 6,1: 0.13: 185: 6,1: 0.14: 185: 6,1: 0.15: 185: 6,1: 0.16: 185: 6, with 0.6320g potassium permanganate totally 7 parts join respectively in the 13mL deionized water, add 0g respectively, 0.0223g, 0.0669g, 0.1115g, 0.1204g, 0.1248g, 0.1382gN-butyl-pyridinium a tetrafluoro borate, be stirred well to the solid dissolving, add the 2mL massfraction more successively and be 36% hydrochloric acid, stir, gained solution is transferred to respectively in the 25mL hydrothermal reaction kettle, 150 ℃ of thermostat(t)ed water thermal responses 36 hours, naturally cool to room temperature, product deionized water wash 3 times placed 50 ℃ of baking ovens dry 6 hours.
By Fig. 4 and Figure 13～18 as seen, when the add-on of N-butyl-pyridinium a tetrafluoro borate is 0g, 0.0223g, 0.0669g, 0.1115g, 0.0669g, 0.1204g, 0.1248g, 0.1382g, the Manganse Dioxide of preparation all has similar hollow polyhedral pattern, size is distributed in 3～5 mu m ranges, when wherein the add-on of N-butyl-pyridinium a tetrafluoro borate is 0.1115g, the polyhedral homogeneity the best of prepared hollow manganese dioxide.
3, the hydro-thermal reaction time is to the influence of Manganse Dioxide pattern
With potassium permanganate, N-butyl-pyridinium a tetrafluoro borate, the mol ratio of deionized water and hydrochloric acid is 1: 0.13: 185: 6, with 0.6320g potassium permanganate and 0.1115g N-butyl-pyridinium a tetrafluoro borate totally 13 parts join respectively in the 13mL deionized water, be stirred well to the solid dissolving, add the 2mL massfraction more successively and be 36% hydrochloric acid, stir, gained solution is transferred in the 25mL hydrothermal reaction kettle, under 150 ℃ of thermostat(t)ed water heat conditions, react 1 respectively, 2,3,6,12,24,36,38,40,42,46,48,60 hours, naturally cool to room temperature, product deionized water wash 3 times placed 50 ℃ of baking ovens dry 6 hours.
By Fig. 4 and Figure 19～30 as seen, hydro- thermal reaction 1,2,3,6 hours, the Manganse Dioxide pattern of preparation is irregular, hydro- thermal reaction 12,24,36,38,40,42,46 hours, the Manganse Dioxide of preparation all has similar hollow polyhedral pattern, the hydro-thermal reaction time is 48 and 60 hours, and prepared Manganse Dioxide is annular pattern.Hydro-thermal reaction is in the time of 36 hours, the polyhedral homogeneity the best of prepared hollow manganese dioxide, and size is distributed in 3～5 mu m ranges.
4, hydrothermal temperature is to the influence of Manganse Dioxide pattern
With potassium permanganate, N-butyl-pyridinium a tetrafluoro borate, the mol ratio of deionized water and hydrochloric acid is 1: 0.13: 185: 6, with 0.6320g potassium permanganate and 0.1115g N-butyl-pyridinium a tetrafluoro borate totally 5 parts join respectively in the 13mL deionized water, be stirred well to the solid dissolving, add the 2mL massfraction more successively and be 36% hydrochloric acid, stir, gained solution is transferred in the 25mL hydrothermal reaction kettle, respectively at 100 ℃, 120 ℃, 140 ℃, 150 ℃ and 160 ℃ of thermostat(t)ed water thermal responses 36 hours, naturally cool to room temperature, product deionized water wash 3 times placed 50 ℃ of baking ovens dry 6 hours.
By Fig. 4 and Figure 31～34 as seen, when hydrothermal temperature was 100 ℃, 120 ℃, the Manganse Dioxide pattern of preparation was irregular, and when hydrothermal temperature was 140 ℃, 150 ℃, 160 ℃, the Manganse Dioxide monarch of preparation had similar hollow polyhedral pattern.When hydrothermal temperature is 150 ℃, the polyhedral homogeneity the best of prepared hollow manganese dioxide, size is distributed in 3～5 mu m ranges.
Claims (3)
1. preparation method of hollow manganese dioxide polyhedron is characterized in that it is made up of following step:
(1) preparation hollow manganese dioxide polyhedron
Mol ratio with potassium permanganate, N-butyl-pyridinium a tetrafluoro borate, deionized water and hydrochloric acid is 1: 0.078～0.16: 185: 4.5～7.2, potassium permanganate and N-butyl-pyridinium a tetrafluoro borate are joined in the deionized water, be stirred well to the solid dissolving, add massfraction again and be 36% hydrochloric acid, stir, gained solution is transferred in the hydrothermal reaction kettle, 140～160 ℃ of thermostat(t)ed water thermal responses 12～46 hours, naturally cools to room temperature;
(2) drying
With product deionized water wash 3 times that step (1) obtains, solid placed 50 ℃ of baking ovens dry 6 hours, was prepared into the hollow manganese dioxide polyhedron.
2. according to the described preparation method of hollow manganese dioxide polyhedron of claim 1, it is characterized in that: in the preparation hollow manganese dioxide polyhedron step (1), the mol ratio of potassium permanganate and N-butyl-pyridinium a tetrafluoro borate, deionized water, hydrochloric acid is 1: 0.13: 185: 6.
3. according to the described preparation method of hollow manganese dioxide polyhedron of claim 1, it is characterized in that: in preparation hollow manganese dioxide polyhedron step (1), gained solution was transferred in the hydrothermal reaction kettle, 150 ℃ of thermostat(t)ed water thermal responses 36 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101878528A CN101844814B (en) | 2010-05-31 | 2010-05-31 | Preparation method of hollow manganese dioxide polyhedron |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101878528A CN101844814B (en) | 2010-05-31 | 2010-05-31 | Preparation method of hollow manganese dioxide polyhedron |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101844814A CN101844814A (en) | 2010-09-29 |
| CN101844814B true CN101844814B (en) | 2011-11-30 |
Family
ID=42769652
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101878528A Expired - Fee Related CN101844814B (en) | 2010-05-31 | 2010-05-31 | Preparation method of hollow manganese dioxide polyhedron |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101844814B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016023399A1 (en) * | 2014-08-13 | 2016-02-18 | 江苏华东锂电技术研究院有限公司 | Negative electrode active material, preparation method therefor, and lithium-ion battery |
| CN105540550A (en) * | 2015-12-23 | 2016-05-04 | 中国电子科技集团公司第四十九研究所 | Preparation method for metal oxide materials |
| CN110277551A (en) * | 2019-06-28 | 2019-09-24 | 陕西科技大学 | One kind is by nonmetallic ion B3+Ion doping MnO2Preparation method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343081B (en) * | 2008-08-25 | 2010-08-18 | 陕西师范大学 | Method of preparing manganese oxide hollow nano-sphere with large-specific surface area |
| 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 |
| CN101624213B (en) * | 2009-08-13 | 2011-05-04 | 陕西师范大学 | Preparation method for manganese dioxide hollow sphere |
-
2010
- 2010-05-31 CN CN2010101878528A patent/CN101844814B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101844814A (en) | 2010-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101624213B (en) | Preparation method for manganese dioxide hollow sphere | |
| CN102126762B (en) | Method for preparing NiO nano flowerlike microspheres with surface topography controllable | |
| Neri et al. | Immobilized β-galactosidase onto magnetic particles coated with polyaniline: Support characterization and galactooligosaccharides production | |
| CN101372363B (en) | Synthetic alpha-MnO 2 Method for micron hollow sphere and nanocluster | |
| CN1315734C (en) | Method for producing nano material of alpha-Fe00H and alpha Fe2O3 in one dimension | |
| CN102476831B (en) | Method for synthesizing OMS-2 manganese oxide octahedral molecular sieve | |
| CN110182860B (en) | Method for preparing nano nickel-sulfur compound by eutectic solvent one-step synthesis method | |
| CN101798120B (en) | Method for producing nanometer iron oxide red by utilizing ferrous chloride recovered from waste acid washing liquor | |
| CN105562017B (en) | A kind of NiFe2O4/SnO2The preparation method of composite photo-catalyst | |
| CN101844814B (en) | Preparation method of hollow manganese dioxide polyhedron | |
| CN110038614A (en) | A kind of nitrogen-doped carbon material and preparation method thereof of cobalt nitride load | |
| CN105967175A (en) | Preparation method of water-soluble fluorinated graphene | |
| CN107185547A (en) | A kind of C/Fe FeVO4Composite photo-catalyst and its preparation method and application | |
| CN103011233B (en) | Method for preparing (Y1-xEux)2(OH)5NO3.nH2O oversized rare-earth layered hydroxide compound particles | |
| CN104818015B (en) | A kind of different metal organic frame luminescent material of picolinic acid class and synthetic method thereof | |
| CN105800571B (en) | A kind of preparation method of two-dimensional nano piece carbon-nitrogen material | |
| CN103373739A (en) | Hydrothermal preparation method of cuprous oxide crystal | |
| CN100577572C (en) | Method for preparing Zn-doped SnO2 micropore nanophase materials | |
| CN100486901C (en) | Synthesis method of cobaltosic oxide nano-tube | |
| CN102328960B (en) | Synthesis method of trimanganese tetroxide material with 3D (three-dimensional) flower-shaped structure | |
| CN105502522A (en) | Preparation method of hollow nickel oxide microspheres | |
| CN106517299A (en) | Sheet-shaped self-assembled basic cupric carbonate flower-type ball and simple preparation method thereof | |
| CN103664965B (en) | A kind of method preparing phthalocyanine micro-nano structure | |
| CN101927146B (en) | Method for preparing In2O3 nano monocrystalline self-assembly microspheres | |
| CN104078187B (en) | Molecule based magnetic materials manganese complex and preparation method thereof |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20111130 Termination date: 20140531 |