CN104310492A - Neodymium cobalt oxide nanorod and preparation method thereof - Google Patents
Neodymium cobalt oxide nanorod and preparation method thereof Download PDFInfo
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- CN104310492A CN104310492A CN201410514824.0A CN201410514824A CN104310492A CN 104310492 A CN104310492 A CN 104310492A CN 201410514824 A CN201410514824 A CN 201410514824A CN 104310492 A CN104310492 A CN 104310492A
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Abstract
The invention discloses a neodymium cobalt oxide nanorod and a preparation method thereof and belongs to the technical field of nano material preparation. The neodymium cobalt oxide nanorod is composed of a single phase NdCoO3 and has the length of being about 1 micron and the diameter of being about 50nm. The preparation method of the neodymium cobalt oxide nanorod is characterized by comprising the following steps: dissolving cobalt salt, neodymium salt and a surfactant in a certain mole ratio into a mixed solvent of water and polyglycol, wherein volume ratio of the water to the polyglycol is 100:(10-20); then heating to 80-100 DEG C, and stirring for at least one hour; then sequentially adding hydrazine hydrate and hydroxide, wherein a mole ratio of the hydrazine hydrate to the water soluble cobalt salt is (1-3):10, and a mole ratio of the hydroxide to the cobalt salt is more than 3:2; reacting for at least 30 minutes; and finally cleaning, and drying, so that the target product neodymium cobalt oxide nanorod is obtained. The preparation method of the neodymium cobalt oxide nanorod has the advantages that a preparation temperature is low, a template does not need to be added, a preparation process is simple, a posttreatment process does not need to be carried out, cost is low, environmental friendliness is realized, and industrial production can be easily realized.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, be specifically related to a kind of neodymium cobalt/cobalt oxide nanometer rod and preparation method thereof.
Background technology
There is the ABO of perovskite structure
3type composite oxides are the very important inorganic functional materials of a class, due to its flexibly chemical tailoring feature and uniqueness physicochemical property and have a wide range of applications in fields such as photoabsorption, catalyzer, solid fuel cell, electrode materials and chemical sensors.Neodymium cobalt/cobalt oxide (NdCoO
3) be a kind of ABO of perovskite structure
3type complex rare-earth oxidate containing valuable metal material, has been applied to many technical fields.As, in environmental catalysis, neodymium cobalt/cobalt oxide is at a lot of catalytic oxidation, the NO that react as CO
xreduction reaction and photochemical catalysis hydro carbons reaction in all show good catalytic activity.When the size of material enters nanometer scale, its surface-area can significantly increase, and can the catalytic performance relying on left and right be had to play the castering action of essence by his-and-hers watches area.There is abundant rare earth resources in China, for making full use of resource, carrying out Sustainable development, advancing the progress of our nanotechnology, and preparation method's Research Significance of carrying out the neodymium cobalt/cobalt oxide nano material of pattern, size and structure-controllable is great.
The people such as Gong Xiaojie (Gong Xiaojie, Li Lihua, Shao Hai, Li Xiuping, Zhang Jinsheng.Microwave-gel method synthesis NdCoO
3nanoparticle.Liaoming Petrochemical Univ's journal, 2005,25 (2): 29-31) utilize microwave-assisted gel method to synthesize NdCoO
3nano particle. the people such as Chen Weifan (Chen Weifan, Liu Leili, Li Fengsheng, Li Yongxiu, Li Huiquan.Salt-assisted?combustion?synthesis?of?NdCoO
3Nanoparticles?and?their?catalytic?properties?in?thermal?decomposition?of?ammonium?perchlorate。Journal of rare earths, 2007,25:21-26.) make use of salt aid burning method and successfully synthesize NdCoO
3nano particle.Chinese invention patent " analyzes the method for crystalline structure of lanthanum rare earth cobalt oxide " with the Raman scattering (patent No.: the lanthanum rare earth cobalt oxide polycrystalline that 200610016825.8) utilized high-temperature solid phase reaction method to prepare, and analyze its crystalline structure with Raman scattering.
The primary synthetic methods of neodymium cobalt/cobalt oxide nano material has: coprecipitation method, high temperature solid-state method and sol-gel method.The particle size of coprecipitation method is comparatively large, cannot effectively control its size distribution; The Spinel that high temperature solid-state method is easy to that neodymium cobalt/cobalt oxide is resolved into a simple oxide and is rich in cobalt; Sol-gel method easily introduces impurity, and phase purity is not high.Neodymium cobalt/cobalt oxide nanometer rod has unique microtexture, and particle diameter is little, length-to-diameter ratio is large, and specific surface area is large, the features such as the contact area of active substance and storeroom can be increased, therefore, controlledly synthesis neodymium cobalt/cobalt oxide nanometer rod, can catalytic performance be improved, cause the research interest of people.Neodymium cobalt/cobalt oxide nanometer rod is expected to become the novel material that nm regime has application potential, but, up to the present also not about the report of neodymium cobalt/cobalt oxide nanometer rod.
Summary of the invention
The object of this invention is to provide a kind of neodymium cobalt/cobalt oxide nanometer rod and preparation method thereof.
The present invention prepares neodymium cobalt/cobalt oxide nanometer rod by NdCoO
3crystal orientation is formed, and mean length is 1 μm, and mean diameter is 50nm.
The preparation method of neodymium cobalt/cobalt oxide nanometer rod provided by the present invention, adopt water soluble cobaltous salt (Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobalt chloride, rose vitriol, Cobaltous diacetate etc.), water-soluble neodymium salt (neodymium nitrate, Neodymium trichloride, Neodymium sulfate, acetic acid neodymium etc.), polyglycol (polyethylene glycol, polypropylene glycol etc.), tensio-active agent (polyethylene oxide, poly(propylene oxide) etc.) is raw material, prepare neodymium cobalt/cobalt oxide nanometer rod by chemical reaction and self assembling process, specifically comprise the following steps:
(1) water soluble cobaltous salt, water-soluble neodymium salt, polyglycol, tensio-active agent are added in solvent successively dissolve;
(2) by step (1) gained mixture, heating, carries out constant temperature stirring;
(3) hydrazine hydrate and water soluble hydroxide are added among step (2) gained mixture, react;
(4) after step (3) gained mixture naturally cools to room temperature, take out supernatant liquid, centrifugation lower sediment, cleaning, dry, obtain neodymium cobalt/cobalt oxide nanometer rod.
In described step (1): water soluble cobaltous salt is selected from any one in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobalt chloride, rose vitriol, Cobaltous diacetate; Described water-soluble neodymium salt is selected from any one in neodymium nitrate, Neodymium trichloride, Neodymium sulfate, acetic acid neodymium; Described polyglycol is selected from the one in polyoxyethylene glycol, polypropylene glycol; Described tensio-active agent is selected from the one in polyethylene oxide, poly(propylene oxide); Described solvent is water and polyglycol mixed solvent, by volume, and water: polyglycol is 100:10 ~ 20; The mol ratio of described water soluble cobaltous salt, water-soluble neodymium salt, tensio-active agent is 100:100:10 ~ 20.
In described step (2): the temperature of heating is 80 ~ 100 DEG C; Churning time at least 1h after constant temperature.
In described step (3): in molar ratio, hydrazine hydrate: water soluble cobaltous salt is 1 ~ 3:10; Described water soluble hydroxide is selected from the one in sodium hydroxide, potassium hydroxide, and the mol ratio of water soluble hydroxide and water soluble cobaltous salt is greater than 3:2; The described reaction times is no less than 30 minutes.
In described step (4): described cleaning repeatedly cleans at least 3 times with water and ethanol successively, and the temperature of described oven dry is 80 ~ 100 DEG C, and the time of described oven dry is 5 ~ 10h.
Relative to prior art, outstanding advantages of the present invention is:
1) the present invention needs not exceed the heating of 100 DEG C, has the advantage reducing production cost and reduce generated time;
2) the present invention is in preparation process without the need to masterplate, and condition is simple, is easy to control, for the practical application of neodymium cobalt/cobalt oxide nanometer rod provides condition;
3) the neodymium cobalt/cobalt oxide nanometer rod purity prepared of the method is high, productive rate is large.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of neodymium cobalt/cobalt oxide nanometer rod prepared by the present invention;
According to JCPDS PDF card (JCPDS card, No.73-1198), gained neodymium cobalt/cobalt oxide nanometer rod can be retrieved by NdCoO
3crystalline phase is formed.
Fig. 2 is scanning electronic microscope (SEM) image of neodymium cobalt/cobalt oxide nanometer rod prepared by the present invention;
As can be seen from the figure products therefrom is nano bar-shape structure, and the length of gained neodymium cobalt/cobalt oxide nanometer rod about 1 μm, diameter is about 50nm.
The high resolution projection electron microscope image of the neodymium cobalt/cobalt oxide nanometer rod of Fig. 3 prepared by the present invention;
As can be seen from the figure the well-regulated lattice fringe of gained neodymium cobalt/cobalt oxide nanometer rod tool, illustrates that this kind of nanometer rod is made up of good monocrystalline.
Embodiment
Below in conjunction with specific embodiment in detail the present invention is described in detail, but the present invention is not limited to following embodiment.
Embodiment 1
By cobalt chloride, Neodymium trichloride, poly-oxepane in molar ratio 100:100:10 dissolve in water and polyethylene glycol mixed solvent, wherein water and polyethylene glycol are 100:10 by volume, are then heated to 80 DEG C, churning time 1h after constant temperature.Then hydrazine hydrate and sodium hydroxide are added successively, wherein hydrazine hydrate and cobalt chloride are 1:10 in molar ratio, and sodium hydroxide and cobalt chloride are 3:2 in molar ratio, and the reaction times is 30 minutes.Finally, cleaning cleans 3 times repeatedly with water and ethanol successively, and the temperature of oven dry is at 80 DEG C, and drying time was at 5 hours.Prepare that length is about 1 μm, diameter is about the neodymium cobalt/cobalt oxide nanometer rod of 50nm.
Embodiment 2
By cobalt chloride, Neodymium trichloride, polyethylene oxide in molar ratio 100:100:15 dissolve in water and polyoxyethylene glycol mixed solvent, wherein water and polyoxyethylene glycol are 100:15 by volume, are then heated to 90 DEG C, churning time 2h after constant temperature.Then hydrazine hydrate and sodium hydroxide are added successively, wherein hydrazine hydrate and cobalt chloride are 2:10 in molar ratio, and sodium hydroxide and cobalt chloride are 3:2 in molar ratio, and the reaction times is 30 minutes.Finally, cleaning cleans 4 times repeatedly with water and ethanol successively, and the temperature of oven dry is at 100 DEG C, and drying time was at 6 hours.Prepare that length is about 1 μm, diameter is about the neodymium cobalt/cobalt oxide nanometer rod of 50nm.
Embodiment 3
By cobalt chloride, Neodymium trichloride, poly(propylene oxide) in molar ratio 100:100:20 dissolve in water and polypropylene glycol mixed solvent, wherein water and polypropylene glycol are 100:20 by volume, are then heated to 100 DEG C, churning time 2h after constant temperature.Then hydrazine hydrate and potassium hydroxide are added successively, wherein hydrazine hydrate and cobalt chloride are 3:10 in molar ratio, and potassium hydroxide and cobalt chloride are 4:2 in molar ratio, and the reaction times is 40 minutes.Finally, cleaning cleans 5 times repeatedly with water and ethanol successively, and the temperature of oven dry is at 90 DEG C, and drying time was at 10 hours.Prepare that length is about 1 μm, diameter is about the neodymium cobalt/cobalt oxide nanometer rod of 50nm.
Embodiment 4
By rose vitriol, Neodymium sulfate, poly(propylene oxide) in molar ratio 100:100:15 dissolve in water and polypropylene glycol mixed solvent, wherein water and polypropylene glycol are 100:15 by volume, are then heated to 90 DEG C, churning time 2h after constant temperature.Then hydrazine hydrate and potassium hydroxide are added successively, wherein hydrazine hydrate and rose vitriol are 2:10 in molar ratio, and potassium hydroxide and rose vitriol are 3:2 in molar ratio, and the reaction times is 50 minutes.Finally, cleaning cleans 6 times repeatedly with water and ethanol successively, and the temperature of oven dry is at 80 DEG C, and drying time was at 8 hours.Prepare that length is about 1 μm, diameter is about the neodymium cobalt/cobalt oxide nanometer rod of 50nm.
Embodiment 5
By rose vitriol, Neodymium sulfate, polyethylene oxide in molar ratio 100:100:15 dissolve in water and polyoxyethylene glycol mixed solvent, wherein water and polyoxyethylene glycol are 100:15 by volume, are then heated to 90 DEG C, churning time 2h after constant temperature.Then hydrazine hydrate and sodium hydroxide are added successively, wherein hydrazine hydrate and rose vitriol are 3:10 in molar ratio, and sodium hydroxide and rose vitriol are 3:2 in molar ratio, and the reaction times is 60 minutes.Finally, cleaning cleans 6 times repeatedly with water and ethanol successively, and the temperature of oven dry is at 80 DEG C, and drying time was at 8 hours.Prepare that length is about 1 μm, diameter is about the neodymium cobalt/cobalt oxide nanometer rod of 50nm.
Embodiment 6
By Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, neodymium nitrate, polyethylene oxide in molar ratio 100:100:20 dissolve in water and polyoxyethylene glycol mixed solvent, wherein water and polyoxyethylene glycol are 100:20 by volume, are then heated to 100 DEG C, churning time 3h after constant temperature.Then hydrazine hydrate and sodium hydroxide are added successively, wherein hydrazine hydrate and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES are 2:10 in molar ratio, and sodium hydroxide and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES are 5:2 in molar ratio, and the reaction times is 60 minutes.Finally, cleaning cleans 3 times repeatedly with water and ethanol successively, and the temperature of oven dry is at 80 DEG C, and drying time was at 10 hours.Prepare that length is about 1 μm, diameter is about the neodymium cobalt/cobalt oxide nanometer rod of 50nm.
Embodiment 7
By Cobaltous diacetate, acetic acid neodymium, poly(propylene oxide) in molar ratio 100:100:15 dissolve in water and polypropylene glycol mixed solvent, wherein water and polypropylene glycol are 100:15 by volume, are then heated to 90 DEG C, churning time 2h after constant temperature.Then hydrazine hydrate and potassium hydroxide are added successively, wherein hydrazine hydrate and Cobaltous diacetate are 2:10 in molar ratio, and potassium hydroxide and Cobaltous diacetate are 3:2 in molar ratio, and the reaction times is 50 minutes.Finally, cleaning cleans 6 times repeatedly with water and ethanol successively, and the temperature of oven dry is at 80 DEG C, and drying time was at 8 hours.Prepare that length is about 1 μm, diameter is about the neodymium cobalt/cobalt oxide nanometer rod of 50nm.
Embodiment 8
By Cobaltous diacetate, acetic acid neodymium, polyethylene oxide in molar ratio 100:100:20 dissolve in water and polyoxyethylene glycol mixed solvent, wherein water and polyoxyethylene glycol are 100:20 by volume, are then heated to 100 DEG C, churning time 3h after constant temperature.Then hydrazine hydrate and sodium hydroxide are added successively, wherein hydrazine hydrate and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES are 2:10 in molar ratio, and sodium hydroxide and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES are 5:2 in molar ratio, and the reaction times is 60 minutes.Finally, cleaning cleans 3 times repeatedly with water and ethanol successively, and the temperature of oven dry is at 80 DEG C, and drying time was at 10 hours.Prepare that length is about 1 μm, diameter is about the neodymium cobalt/cobalt oxide nanometer rod of 50nm.
Embodiment 9
By Cobaltous diacetate, acetic acid neodymium, poly-oxepane in molar ratio 100:100:10 dissolve in water and polyethylene glycol mixed solvent, wherein water and polyethylene glycol are 100:10 by volume, are then heated to 80 DEG C, churning time 1h after constant temperature.Then hydrazine hydrate and sodium hydroxide are added successively, wherein hydrazine hydrate and Cobaltous diacetate are 1:10 in molar ratio, and sodium hydroxide and Cobaltous diacetate are 3:2 in molar ratio, and the reaction times is 30 minutes.Finally, cleaning cleans 3 times repeatedly with water and ethanol successively, and the temperature of oven dry is at 80 DEG C, and drying time was at 5 hours.Prepare that length is about 1 μm, diameter is about the neodymium cobalt/cobalt oxide nanometer rod of 50nm.
Claims (2)
1. a neodymium cobalt/cobalt oxide nanometer rod, is characterized in that, this neodymium cobalt/cobalt oxide nanometer rod is by NdCoO
3single-phase formation, mean length is 1 μm, and mean diameter is 50nm.
2. the preparation method of neodymium cobalt/cobalt oxide nanometer rod as claimed in claim 1, is characterized in that comprising the steps:
(1) water soluble cobaltous salt, water-soluble neodymium salt, polyglycol, tensio-active agent are added in solvent successively dissolve;
(2) by step (1) gained mixture, heating, carries out constant temperature stirring;
(3) hydrazine hydrate and water soluble hydroxide are added among step (2) gained mixture, react;
(4) after step (3) gained mixture naturally cools to room temperature, take out supernatant liquid, centrifugation lower sediment, cleaning, dry, obtain neodymium cobalt/cobalt oxide nanometer rod;
In described step (1): water soluble cobaltous salt is selected from any one in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobalt chloride, rose vitriol, Cobaltous diacetate; Described water-soluble neodymium salt is selected from any one in neodymium nitrate, Neodymium trichloride, Neodymium sulfate, acetic acid neodymium; Described polyglycol is selected from the one in polyoxyethylene glycol, polypropylene glycol; Described tensio-active agent is selected from the one in polyethylene oxide, poly(propylene oxide); Described solvent is water and polyglycol mixed solvent, by volume, and water: polyglycol is 100:10 ~ 20; The mol ratio of described water soluble cobaltous salt, water-soluble neodymium salt, tensio-active agent is 100:100:10 ~ 20;
In described step (2): the temperature of heating is 80 ~ 100 DEG C; Churning time at least 1h after constant temperature;
In described step (3): in molar ratio, hydrazine hydrate: water soluble cobaltous salt is 1 ~ 3:10; Described water soluble hydroxide is selected from the one in sodium hydroxide, potassium hydroxide, and the mol ratio of water soluble hydroxide and water soluble cobaltous salt is greater than 3:2; The described reaction times is no less than 30 minutes;
In described step (4): described cleaning repeatedly cleans at least 3 times with water and ethanol successively, and the temperature of described oven dry is 80 ~ 100 DEG C, and the time of described oven dry is 5 ~ 10h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101723434A (en) * | 2008-10-22 | 2010-06-09 | 国家纳米科学中心 | Ternary oxide nano material, ternary oxide nano structure and preparation method thereof |
| CN102664103A (en) * | 2012-03-31 | 2012-09-12 | 华中科技大学 | Zinc cobaltate nanorod/foam nickel composite electrode, preparation method thereof and application thereof |
| CN103011264A (en) * | 2012-12-19 | 2013-04-03 | 黑龙江大学 | Preparation method of one-dimensional metal titanate nanorods |
| US20140256534A1 (en) * | 2011-09-28 | 2014-09-11 | University Of Connecticut | Metal oxide nanorod arrays on monolithic substrates |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723434A (en) * | 2008-10-22 | 2010-06-09 | 国家纳米科学中心 | Ternary oxide nano material, ternary oxide nano structure and preparation method thereof |
| US20140256534A1 (en) * | 2011-09-28 | 2014-09-11 | University Of Connecticut | Metal oxide nanorod arrays on monolithic substrates |
| CN102664103A (en) * | 2012-03-31 | 2012-09-12 | 华中科技大学 | Zinc cobaltate nanorod/foam nickel composite electrode, preparation method thereof and application thereof |
| CN103011264A (en) * | 2012-12-19 | 2013-04-03 | 黑龙江大学 | Preparation method of one-dimensional metal titanate nanorods |
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