CN104229905A - Preparation method of multi-duct cobalt hydroxide flower-shaped microspheres - Google Patents
Preparation method of multi-duct cobalt hydroxide flower-shaped microspheres Download PDFInfo
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- CN104229905A CN104229905A CN201410455213.3A CN201410455213A CN104229905A CN 104229905 A CN104229905 A CN 104229905A CN 201410455213 A CN201410455213 A CN 201410455213A CN 104229905 A CN104229905 A CN 104229905A
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Abstract
The invention provides a preparation method of multi-duct cobalt hydroxide flower-shaped microspheres, and belongs to the technical field of nano material synthesis. The preparation method comprises the following steps: uniformly mixing organic cobalt, deionized water and hexamethylene tetramine, and then transferring the mixture to a reaction kettle with a polytetrafluoroethylene lining; after carrying out a hydrothermal reaction at a low temperature, centrifugally separating, washing and drying hydrothermal products to prepare the multi-duct cobalt hydroxide flower-shaped microspheres. According to the preparation method of the multi-duct cobalt hydroxide flower-shaped microsphere, the deionized water is taken as a solvent, and the flower-shaped microspheres with a relatively high yield and a uniform morphology are prepared by adopting a hydrothermal synthesis process, and the flower-shaped microspheres can be used for preparing an electrode material of a storage battery. The preparation method is simple in process, relatively low in a synthesis temperature, free of a template agent and good in repeatability, so that the energy consumption and the reaction cost are lowered, and mass production is convenient.
Description
Technical field
The invention belongs to nano material synthesis technical field, be specifically related to the method that the preparation of a kind of hydrothermal method has the cobaltous hydroxide of multi-pore channel flower-like microsphere pattern.
Background technology
All the time, the morphology control of inorganic nano material all obtains investigator and pays close attention to especially.Cobaltous hydroxide, owing to having unique physicochemical property, as having laminate structure and good electrochemical redox performance etc., therefore has a wide range of applications in the field such as catalysis, electrochemistry.The pattern of cobaltous hydroxide has important impact to its properties and application.Up to now, people have carried out large quantifier elimination for the morphology control of cobaltous hydroxide, and successfully synthesize one dimension and two-dirnentional structure (Nature, 458,746-749,2009 such as nanometer sheet, nano wire, nanometer rod; Nanoscale, 1,50-60,2009; J.SolidStateChem., 184,2961-2965,2011).But its three-dimensional structure is still reported less, and the certain methods used mostly needs to adopt template (CN102807255A), thus increases preparation cycle and the cost of material.Therefore, develop simple and easy reliable and without the need to using the method for template to be very necessary to synthesize multidimensional material, be also a significant challenge in current materials synthesis.The present invention is intended to utilize hydro-thermal reaction, and pattern and size in lower temperature and without the need to controlling material under adopting the condition of template, synthesize the cobaltous hydroxide flower-like microsphere of multi-pore channel.The present invention has no document and patent report.
Summary of the invention
In recent years, people have carried out large quantifier elimination to the pattern of cobaltous hydroxide, and successfully synthesize nanometer sheet, nano wire, the low dimensional structures such as nanometer rod; But its three-dimensional structure rarely has report, and obtain three-dimensional structure by self-assembly mode and usually need to adopt template, thus increase the preparation cost of material and the purifying difficulty of subsequent products.The object of this invention is to provide a kind of simple method for preparing of cobaltous hydroxide porous flower-like microsphere.Organic cobalt and vulkacit H are dispersed in aqueous phase; Wherein, vulkacit H slowly releases hydroxide ion under certain temperature condition, and the organic acid anions in organic cobalt also plays the effect of structure directing agent simultaneously, impel cobalt ion and hydroxide radical particle orientation response to form multi-pore channel hydroxide flake cobalt, and then self-assembly form multi-pore channel flower-like microsphere.Organic cobalt used is cobalt oxalate or cobaltous acetate.
For achieving the above object, the technical solution used in the present invention is for mix organic cobalt, vulkacit H, deionized water and to be transferred in teflon-lined reactor, after the hydro-thermal reaction of lesser temps, by obtained after hydrothermal product centrifugation, washing, drying.
Hydrothermal method prepares the method for multi-pore channel cobaltous hydroxide flower-like microsphere, specifically comprises the following steps:
Steps A, organic cobalt and vulkacit H join in aqueous phase, and at 25-60 DEG C, stirring and dissolving forms solution;
Step B, above-mentioned solution to be transferred in teflon-lined reactor constant temperature 12-48 hour at 80-120 DEG C, obtain hydrothermal product after naturally cooling;
Step C, above-mentioned hydrothermal product carry out centrifugation, and the solid matter with deionized water after centrifugal and acetone wash 1-3 time respectively;
Step D, by above-mentioned solid product dry 6-12 hour at 50-100 DEG C in vacuum drying oven, finally obtain blue multi-pore channel cobaltous hydroxide flower-like microsphere.
In a preference of the present invention, described reactant is according to cobaltous acetate or cobalt oxalate: vulkacit H: the molar ratio of deionized water is 2-10:2-10:80-96 mixing.
The reagent that the present invention participates in reacting is analytical pure, commercially available.
The multi-pore channel cobaltous hydroxide flower-like microsphere thickness obtained according to method disclosed by the invention is 1-100 nanometer, and channel diameter is that the cobaltous hydroxide nanometer sheet self-assembly of 10-100 nanometer is formed, and the diameter of flower-like microsphere is 1-10 micron.
In the present invention, the vesicular structure of cobaltous hydroxide is determined by low-temperature physics adsorption tester, and low temperature nitrogen adsorption desorption curve and graph of pore diameter distribution show, this material has abundant pore passage structure.
Tungsten filament sem test shows, combine with the self-assembling technique diameter of the cobaltous hydroxide flower-like microsphere prepared of hydro-thermal reaction is 1-10 micron, and be 1-100 nanometer by thickness, channel diameter is that the cobaltous hydroxide nanometer sheet self-assembly of 10-100 nanometer is formed.
X-ray powder diffraction shows, the combine flower-like microsphere of preparation of hydro-thermal reaction and self-assembling technique has the characteristic diffraction peak of typical cobaltous hydroxide, and does not have the diffraction peak of other materials in collection of illustrative plates, illustrates that product is pure phase cobaltous hydroxide.
Beneficial effect of the present invention is: utilize hydrothermal synthesis method, under relatively mild temperature of reaction and without the need to adopting template one step to prepare the higher and multi-pore channel cobaltous hydroxide three-dimensional material that pattern is comparatively homogeneous of productive rate, this materials chemistry stability is better, can be used as electrode materials or the catalytic material of preparing store battery.Present invention process is simple, mild condition, favorable reproducibility and without the need to using template, therefore short, the energy consumption of preparation cycle and cost low and simple to operate, be convenient to batch production.
Accompanying drawing explanation
The nitrogen adsorption desorption curve of the cobaltous hydroxide flower-like microsphere that Fig. 1 embodiment 1 is obtained and graph of pore diameter distribution.
The scanning electron microscope (SEM) photograph of the cobaltous hydroxide flower-like microsphere that Fig. 2 embodiment 1 is obtained.
The X-ray powder diffraction of the cobaltous hydroxide flower-like microsphere that Fig. 3 embodiment 1 is obtained.
Embodiment
In order to explain the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment 1
The preparation process of multi-pore channel cobaltous hydroxide flower-like microsphere is as follows:
A. the vulkacit H of 0.02mol cobaltous acetate and 0.02mol is joined in the deionized water of 0.96mol, Keep agitation at 25 DEG C, until dissolve completely;
B. be transferred in teflon-lined reactor by above-mentioned solution, constant temperature 12 hours at 80 DEG C, then naturally cooling, obtains hydrothermal product;
C. hydrothermal product obtained above is carried out centrifugation, wash 3 times respectively with deionized water and acetone;
D. within 12 hours, namely final product is obtained by dry at 50 DEG C in vacuum drying oven for the product after centrifuge washing.
The low temperature nitrogen adsorption desorption curve that Fig. 1 shows product belongs to typical IV type adsorption desorption curve, and its graph of pore diameter distribution also shows have duct to exist in product, and channels diameter range is in 10-100 nanometer.
The cobaltous hydroxide flower-like microsphere diameter prepared as can be seen from Figure 2 is 2-10 micron, is be 1-100 nanometer by thickness, and channel diameter is that the cobaltous hydroxide nanometer sheet self-assembly of 10-100 nanometer is formed.
In Fig. 3, the position of each diffraction peak is blocked consistent with relative intensity with JCPDS (30-443), and occurs without obvious impurity peaks, shows that the product prepared is the cobaltous hydroxide of pure phase.
Embodiment 2
The preparation process of multi-pore channel cobaltous hydroxide flower-like microsphere is as follows:
A. the vulkacit H of 0.02mol cobalt oxalate and 0.02mol is joined in the deionized water of 0.96mol, Keep agitation at 25 DEG C, until dissolve completely;
B. be transferred in teflon-lined reactor by above-mentioned solution, constant temperature 12 hours at 80 DEG C, then naturally cooling, obtains hydrothermal product;
C. hydrothermal product obtained above is carried out centrifugation, wash 3 times respectively with deionized water and acetone;
D. within 12 hours, namely final product is obtained by dry at 50 DEG C in vacuum drying oven for the product after centrifuge washing.
Embodiment 3
The preparation process of multi-pore channel cobaltous hydroxide flower-like microsphere is as follows:
A. the vulkacit H of 0.02mol cobaltous acetate and 0.02mol is joined in the deionized water of 0.96mol, Keep agitation at 25 DEG C, until dissolve completely;
B. be transferred in teflon-lined reactor by above-mentioned solution, constant temperature 12 hours at 120 DEG C, then naturally cooling, obtains hydrothermal product;
C. hydrothermal product obtained above is carried out centrifugation, wash 3 times respectively with deionized water and acetone;
D. within 12 hours, namely final product is obtained by dry at 50 DEG C in vacuum drying oven for the product after centrifuge washing.
Embodiment 4
The preparation process of multi-pore channel cobaltous hydroxide flower-like microsphere is as follows:
A. the vulkacit H of 0.10mol cobaltous acetate and 0.10mol is joined in the deionized water of 0.80mol, Keep agitation at 25 DEG C, until dissolve completely;
B. be transferred in teflon-lined reactor by above-mentioned solution, constant temperature 12 hours at 120 DEG C, then naturally cooling, obtains hydrothermal product;
C. hydrothermal product obtained above is carried out centrifugation, wash 3 times respectively with deionized water and acetone;
D. within 12 hours, namely final product is obtained by dry at 50 DEG C in vacuum drying oven for the product after centrifuge washing.
Embodiment 5
The preparation process of multi-pore channel cobaltous hydroxide flower-like microsphere is as follows:
A. the vulkacit H of 0.02mol cobaltous acetate and 0.02mol is joined in the deionized water of 0.96mol, Keep agitation at 60 DEG C, until dissolve completely;
B. be transferred in teflon-lined reactor by above-mentioned solution, constant temperature 12 hours at 80 DEG C, then naturally cooling, obtains hydrothermal product;
C. hydrothermal product obtained above is carried out centrifugation, wash 3 times respectively with deionized water and acetone;
D. within 12 hours, namely final product is obtained by dry at 50 DEG C in vacuum drying oven for the product after centrifuge washing.
Embodiment 6
The preparation process of multi-pore channel cobaltous hydroxide flower-like microsphere is as follows:
A. the vulkacit H of 0.02mol cobaltous acetate and 0.02mol is joined in the deionized water of 0.96mol, Keep agitation at 60 DEG C, until dissolve completely;
B. be transferred in teflon-lined reactor by above-mentioned solution, constant temperature 48 hours at 80 DEG C, then naturally cooling, obtains hydrothermal product;
C. hydrothermal product obtained above is carried out centrifugation, wash 3 times respectively with deionized water and acetone;
D. within 12 hours, namely final product is obtained by dry at 50 DEG C in vacuum drying oven for the product after centrifuge washing.
Embodiment 7
The preparation process of multi-pore channel cobaltous hydroxide flower-like microsphere is as follows:
A. the vulkacit H of 0.02mol cobaltous acetate and 0.02mol is joined in the deionized water of 0.96mol, Keep agitation at 25 DEG C, until dissolve completely;
B. be transferred in teflon-lined reactor by above-mentioned solution, constant temperature 12 hours at 80 DEG C, then naturally cooling, obtains hydrothermal product;
C. hydrothermal product obtained above is carried out centrifugation, wash 1 time respectively with deionized water and acetone;
D. within 12 hours, namely final product is obtained by dry at 50 DEG C in vacuum drying oven for the product after centrifuge washing.
Embodiment 8
The preparation process of multi-pore channel cobaltous hydroxide flower-like microsphere is as follows:
A. the vulkacit H of 0.02mol cobaltous acetate and 0.02mol is joined in the deionized water of 0.96mol, Keep agitation at 25 DEG C, until dissolve completely;
B. be transferred in teflon-lined reactor by above-mentioned solution, constant temperature 12 hours at 80 DEG C, then naturally cooling, obtains hydrothermal product;
C. hydrothermal product obtained above is carried out centrifugation, wash 1 time respectively with deionized water and acetone;
Within 6 hours, namely final product is obtained by dry at 100 DEG C in vacuum drying oven for the product after centrifuge washing.
Claims (5)
1. a preparation method for the cobaltous hydroxide of multi-pore channel flower-like microsphere pattern, is characterized in that comprising the steps:
Steps A, organic cobalt and vulkacit H join in aqueous phase, and at 25-60 DEG C, stirring and dissolving forms solution;
Step B, above-mentioned solution are transferred in teflon-lined reactor, and at 80-120 DEG C, constant temperature 12-48 hour, obtains hydrothermal product after naturally cooling;
Step C, above-mentioned hydrothermal product carry out centrifugation, and the solid matter with deionized water after centrifugal and acetone wash 1-3 time respectively;
Step D, by above-mentioned solid product dry 6-12 hour at 50-100 DEG C in vacuum drying oven, finally obtain blue multi-pore channel cobaltous hydroxide flower-like microsphere.
2. the preparation method of the cobaltous hydroxide of a kind of multi-pore channel flower-like microsphere pattern according to claim 1, it is characterized in that, in described steps A, organic cobalt is cobaltous acetate or cobalt oxalate.
3. the preparation method of the cobaltous hydroxide of a kind of multi-pore channel flower-like microsphere pattern according to claim 1, is characterized in that, organic cobalt in described reactant: vulkacit H: the molar ratio of deionized water is 2-10:2-10:80-96 mixing.
4. the preparation method of the cobaltous hydroxide of a kind of multi-pore channel flower-like microsphere pattern according to claim 1, is characterized in that: described flower-like microsphere is 1-100 nanometer by thickness, and channel diameter is that the cobaltous hydroxide nanometer sheet self-assembly of 10-100 nanometer is formed.
5. the preparation method of the cobaltous hydroxide of a kind of multi-pore channel flower-like microsphere pattern according to claim 1, is characterized in that: the diameter of described flower-like microsphere is 1-10 micron.
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Cited By (5)
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| CN106219615A (en) * | 2016-08-23 | 2016-12-14 | 肖洋 | The preparation method of flower-shaped cobalt hydroxide microsphere |
| CN106876695A (en) * | 2017-03-10 | 2017-06-20 | 上海应用技术大学 | A kind of spherical Co (OH)2Combination electrode material and preparation method thereof |
| CN107098402A (en) * | 2017-05-10 | 2017-08-29 | 郑州大学 | A kind of α Co (OH) of nanometer flower structure with holes2And its production and use |
| CN107240509A (en) * | 2017-06-01 | 2017-10-10 | 上海应用技术大学 | A kind of preparation method of N doping capsule structure carbon material |
| CN108057461A (en) * | 2016-11-07 | 2018-05-22 | 中国科学院大连化学物理研究所 | A kind of cobalt hydroxide catalyst of organic group intercalation modification and its preparation and application |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106219615A (en) * | 2016-08-23 | 2016-12-14 | 肖洋 | The preparation method of flower-shaped cobalt hydroxide microsphere |
| CN108057461A (en) * | 2016-11-07 | 2018-05-22 | 中国科学院大连化学物理研究所 | A kind of cobalt hydroxide catalyst of organic group intercalation modification and its preparation and application |
| CN106876695A (en) * | 2017-03-10 | 2017-06-20 | 上海应用技术大学 | A kind of spherical Co (OH)2Combination electrode material and preparation method thereof |
| CN106876695B (en) * | 2017-03-10 | 2019-12-03 | 上海应用技术大学 | A kind of spherical Co (OH)2Combination electrode material and preparation method thereof |
| CN107098402A (en) * | 2017-05-10 | 2017-08-29 | 郑州大学 | A kind of α Co (OH) of nanometer flower structure with holes2And its production and use |
| CN107098402B (en) * | 2017-05-10 | 2019-06-14 | 郑州大学 | A kind of α-Co (OH) of nanometer flower structure with holes2And its preparation method and application |
| CN107240509A (en) * | 2017-06-01 | 2017-10-10 | 上海应用技术大学 | A kind of preparation method of N doping capsule structure carbon material |
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Application publication date: 20141224 |