CN102807255A - Flower-like nanometer cobalt hydroxide material and preparation method thereof - Google Patents
Flower-like nanometer cobalt hydroxide material and preparation method thereof Download PDFInfo
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Abstract
Disclosed are a flower-like nanometer cobalt hydroxide material and a preparation method thereof. The material is synthesized by the self-assembling method. The preparation method includes that metallic cobalt is reacted with alkali in an oil and water double-phase system at the room temperature, and the flower-like nanometer cobalt hydroxide material is prepared under a guiding effect and a wrapping effect of a soft template with the participation of the soft template. The preparation method is simple to operate and easy to control. The size of a multi-dimensional structure a prepared cobalt hydroxide nanoflower ranges from 300 nanometers to 500 nanometers approximately, the multi-dimensional structure of the nanoflower is self-assembled by cobalt hydroxide plates, and the nanoflower is high in specific surface area and pore volume, and can be applied to fields of battery materials, catalytic materials and the like.
Description
Technical field
The invention belongs to nano material, specifically a kind of nano metal cobalt hydroxide material and preparation thereof with floriform appearance.
Background technology
In recent years, be focus of material synthetic through the synthetic multidimensional structure material of self-assembly, morphology control is a key issue of present complex functionality material.Because cobaltous hydroxide has the character of unique physics and chemistry, such as having laminate structure and good electrochemical redox performance, in catalysis, fields such as electrochemistry and vapor phase sensor have a wide range of applications, and have caused people's extensive interest.The pattern of cobaltous hydroxide is to its performance and application important influence.The pattern of cobaltous hydroxide obtains a large amount of research, success synthesized one-dimentional structures such as nanometer sheet, nano wire, nanometer rod, nanotube.But three bit architectures report but seldom.Though the cobaltous hydroxide multidimensional structure of the hollow ball of self-assembly and various patterns also will report, but these multidimensional structures all in microscopic dimensions, the cobaltous hydroxide multidimensional structure of the Nano grade that self-assembly forms rarely has report.Nano material spills more active sites cruelly, thereby has more novel performance, and synthesis of nano multidimensional material has great importance, and also is a kind of challenge during material synthesizes.The present invention is intended to utilize the soft template effect, in the profit two-phase system, and the pattern of control material and size, synthetic cobaltous hydroxide nanometer flower multidimensional structure.The present invention does not see document and patent report.
Summary of the invention
In recent years, the pattern of cobaltous hydroxide obtains a large amount of research, success synthesized one-dimentional structures such as nanometer sheet, nano wire, nanometer rod, nanotube.But three-dimensional structure report is but seldom, and these multidimensional structures all in the microscopic dimensions size more than several microns, self-assembly form a micron once the cobaltous hydroxide multidimensional structure rarely have report.The purpose of this invention is to provide a kind of cobaltous hydroxide nanometer floral material and preparation method thereof.In order to make cobalt ion and precipitation agent alkali uniform contact; Obtain big or small homogeneous material, the present invention adopts tensio-active agent and cosurfactant that the cobalt aqueous solution and inorganic base aqueous solution are dispersed in respectively among the oil phase, slowly in the cobalt microemulsion, drips alkali; Full contact, precipitation from homogeneous solution.Tensio-active agent also plays the effect of soft template; Utilize its guide effect and package action; The pattern of control material and size, the one-dimentional structure cobaltous hydroxide nanometer sheet of generation is assembled into the nanometer floral material of three-dimensional structure under the soft template guide effect, simultaneously under the physics package action of soft template; The gathering of limiting material is grown up, and the control material size is at Nano grade.Used soft template is linear alkylbenzene sulphonic acid or the α-sodium olefin sulfonate in the AS; Or be Np series or the tween series of surfactants in the nonionogenic tenside, or be the CTAB in the cats product.
For realizing above-mentioned purpose, the technical scheme that the present invention adopts is:
In the presence of soft template, synthetic through the method for self-assembly; In the profit two-phase system, cobalt metal and alkali uniform contact, reaction utilize the guide effect of soft template and package action to prepare under the room temperature.
Can operate as follows:
1) inorganic salt and precipitation agent high dispersive in oil phase: tensio-active agent, cosurfactant and organic phase are mixed composition reverse micro emulsion A; The aqueous solution and the inorganic base aqueous solution of metal soluble salt are joined profit two-phase system B and the C that obtains high dispersive among the A respectively respectively; Organic amine is dissolved in and is solution D in the organic phase.
2) precipitation from homogeneous solution: when using mineral alkali, under the agitation condition, C slowly is added drop-wise among the B, stirs 1-24h; When using organic amine as alkali, D slowly is added drop-wise among the B, stir 1-24h.
3) material cleans: centrifugal collection solid; With washing with alcohol 2-time, remove tensio-active agent, 50-150 ℃ of oven dry finally obtains green cobaltous hydroxide nanometer floral material;
The mass ratio of gained final blending solution is 0～10 tensio-active agent: 1～6 water: 5～15 organic phases: 0～6 cosurfactant: 1 metal-salt; Alkali and metal-salt mol ratio are 0.5-3.
Among the said cobaltous hydroxide nanometer floral material preparation method, chlorate, acetate, nitrate salt, vitriol that said metal soluble salt is a metal; Said organic phase is hexanaphthene, normal hexane or toluene; Cosurfactant is propyl carbinol, Pentyl alcohol, n-hexyl alcohol or n-Octanol.Said alkali is mineral alkali, like ammoniacal liquor, and sodium hydroxide and organic bases, like organic amine, organic amine can be an alkylamine, dialkylamine and trialkylamine.
The present invention has following advantage:
A kind of nanoflakes and cobalt hydroxide material with floriform appearance is to pile up the three-dimensional structure that forms by the cobaltous hydroxide nanometer sheet, and the three-dimensional structure that this gathering forms presents floriform appearance, promptly forms the nanometer flower, and nanometer flower particle diameter is 300-500nm nanometer (seeing Fig. 2 and Fig. 3).This compound method is done simple, easily control.Have higher specific surface area and pore volume,, have potential application in the fields such as catalysis therefore at battery.
Description of drawings
The x-ray diffractogram of powder of Fig. 1 nanoflakes and cobalt hydroxide materials A;
The transmission electron microscope photo of Fig. 2 nanoflakes and cobalt hydroxide materials A;
The stereoscan photograph of Fig. 3 nanoflakes and cobalt hydroxide materials A.
Embodiment
A certain proportion of tensio-active agent, cosurfactant and organic phase are mixed the composition solution A; The aqueous solution and the inorganic base aqueous solution of metal soluble salt are joined profit two-phase system B and the C that obtains high dispersive among the A respectively respectively; Organic amine is dissolved in and is solution D in the organic phase.When using inorganic base aqueous solution, under the agitation condition, C slowly is added drop-wise among the B, stir 1-24h.When using organic amine as alkali, D slowly is added drop-wise among the B, stir 1-24h.Centrifugal collection solid is removed tensio-active agent with 2-6 this solid of washing of ethanol, and 80-150 ℃ of oven dry finally obtains green cobaltous hydroxide nanometer floral material; The mass ratio of gained final blending solution is 0～10 tensio-active agent: 1～6 water: 5～15 organic phases: 0～6 cosurfactant: 1 metal-salt; Alkali and metal-salt mol ratio are 0.5-3.
Through embodiment method provided by the invention is detailed below, but do not limit the present invention in any form.
The preparation of embodiment 1 materials A
Get 5g Np-12,5g hexanaphthene and 3g n-Octanol mix solution A; The 1g Cobaltous diacetate is dissolved in the 3g deionized water, adds among the A to obtain two system B of profit, and 1g ammoniacal liquor (25-28%) is dissolved among the 2g water adding A and obtains two system C of profit, stirs down, solution C is slowly splashed into B, aging 2h; Then, the centrifugal solid that gets; In this solid, add 30mL ethanol, heated and stirred 10min is centrifugal; Repeat this step repeatedly, clean until removal of surfactant; 80 ℃ dry final nano material.The The Nomenclature Composition and Structure of Complexes of materials A proves α-Co (OH) through powder x-ray diffraction (XRD)
2Pure phase (Fig. 1).Can find out that from transmission electron microscope picture (Fig. 2) and ESEM (Fig. 3) the cobaltous hydroxide multidimensional structure is formed by the gathering of cobaltous hydroxide nanometer sheet, whole aggregate presents floriform appearance, and about 300-500nm is better dispersed.
The preparation of embodiment 2 material B
Get 1g X 2073,6g toluene, 2g n-hexyl alcohol mix solution A; The 1g Xiao Suangu be dissolved in the 2g deionized water solution B, add among the A and obtain two system B of profit, and add 0.03g sodium hydroxide and be dissolved in 2g water and add among the A and obtain two system C of profit, stir down, solution C is slowly splashed among the B aging 10h; Then, the centrifugal solid that gets; In this solid, add 30ml ethanol, heated and stirred 10min is centrifugal; Repeat this step repeatedly, clean until removal of surfactant; 80 ℃ dry final nano material.
The preparation of embodiment 3 material C
Get 4g CTAB, 12g normal hexane, 4g n-hexyl alcohol mix solution A; The 1g NSC 51149 is dissolved in and gets solution B in the 3g deionized water; Obtain two system B of profit among the adding A, the 0.4g n-Butyl Amine 99 is dissolved in the 3g normal hexane and obtains solution D.Stir down, solution D is slowly splashed among the B, aging 1h; Then, the centrifugal solid that gets; In this solid, add 30ml ethanol, heated and stirred 10min is centrifugal; Repeat this step repeatedly, clean until removal of surfactant; 80 ℃ dry final nano material.
The preparation of embodiment 4 material D
Get 10g tween-80,12g normal hexane, 4g Pentyl alcohol mix solution A; The 1g rose vitriol is dissolved in and gets solution B in the 3g deionized water; Obtain two system B of profit among the adding A, the 1.4g Tributylamine is dissolved in the 6g normal hexane and obtains solution D.Stir down, solution D is slowly splashed among the B, aging 2h; Then, the centrifugal solid that gets; In this solid, add 30ml ethanol, heated and stirred 10min is centrifugal; Repeat this step repeatedly, clean until removal of surfactant; 80 ℃ dry final nano material.
The nanostructure of these nano particles and pattern can pass through powder x-ray diffraction (XRD); ESEM (SEM) and projection Electronic Speculum means such as (TEM) prove; Can find out that from Electronic Speculum figure the cobaltous hydroxide multidimensional structure has flower dress pattern, is formed by the self-assembly of cobaltous hydroxide nanometer sheet; About 300-500nm, better dispersed.This method synthetic cobaltous hydroxide nano material has high specific surface area and pore volume, and in catalysis, there is potential application in fields such as electrochemistry and vapor phase sensor.
Claims (5)
1. nanoflakes and cobalt hydroxide material with floriform appearance is characterized in that:
Be to pile up the three-dimensional structure that forms by the cobaltous hydroxide nanometer sheet, the three-dimensional structure that this gathering forms presents floriform appearance, promptly forms the nanometer flower, and nanometer flower particle diameter is the 300-500nm nanometer.
2. according to the said nanoflakes and cobalt hydroxide material of claim 1, it is characterized in that: the multidimensional structure that said nanometer flower has is to be formed by the self-assembly of cobaltous hydroxide nanometer sheet;
In the presence of soft template, synthetic through the method for self-assembly; In the profit two-phase system, cobalt metal and alkali uniform contact, reaction utilize the guide effect of soft template and package action to prepare under the room temperature.
3. said cobaltous hydroxide preparation methods of claim 1 is characterized in that: can operate as follows:
1) inorganic salt and precipitation agent high dispersive in oil phase: tensio-active agent, cosurfactant and organic phase are mixed the composition solution A;
The aqueous solution of metal soluble salt is joined the profit two-phase system B that obtains high dispersive among the A respectively;
Inorganic base aqueous solution is joined the profit two-phase system C that obtains high dispersive among the A respectively; Or organic amine is dissolved in the organic phase is solution D;
2) precipitation from homogeneous solution:
When using mineral alkali, under the agitation condition, C slowly is added drop-wise among the B, stir 1-24h; Centrifugal collection solid;
Maybe when using organic amine, D slowly is added drop-wise among the B, stirs 1-24h as alkali; Centrifugal collection solid;
4) material cleans: solid is removed tensio-active agent with washing with alcohol 2-6 time, and 50-150 ℃ of oven dry finally obtains the cobaltous hydroxide nanometer floral material of green;
In the precipitation from homogeneous solution process, the mass ratio of each material is 0～10 tensio-active agent among final blending solution D+B or the C+B: 1～6 water: 5～15 organic phases: 0～6 cosurfactant: 1 metal-salt; Alkali and metal-salt mol ratio are 0.5-3.
4. according to the described preparation method of claim 3; It is characterized in that: said tensio-active agent is linear alkylbenzene sulphonic acid or the α-sodium olefin sulfonate in the AS; Or be Np series or the tween series of surfactants in the nonionogenic tenside; Or be the CTAB in the cats product, it is a soft template;
Said organic phase is hexanaphthene, normal hexane or toluene;
Cosurfactant is, propyl carbinol, Pentyl alcohol, n-hexyl alcohol or n-Octanol.
5. according to the described preparation method of claim 3, it is characterized in that: a kind of in the muriate that said metal soluble salt is a cobalt metal, acetate, nitrate salt, the vitriol or more than two kinds;
Mineral alkali is ammoniacal liquor or sodium hydroxide; Organic bases is an alkylamine, dialkylamine or trialkylamine.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232076A (en) * | 2013-05-16 | 2013-08-07 | 漳州师范学院 | Synthesis method of cobalt hydroxide with different grain diameters |
| CN104001523A (en) * | 2014-06-06 | 2014-08-27 | 安徽师范大学 | Cobalt/noble metal/cobalt hydroxide nano-composite material, and preparation method and application thereof |
| CN104671293A (en) * | 2015-02-02 | 2015-06-03 | 浙江大学 | Hierarchically layered monometal hydroxide as well as synthesis method and application thereof |
| CN106711432A (en) * | 2016-12-21 | 2017-05-24 | 中南大学 | MoO2 nano material with three-dimensional network structure and preparation and application thereof |
| KR101794454B1 (en) | 2016-07-18 | 2017-11-07 | 동국대학교 산학협력단 | Method of manufacturing a cobalt having a hierarchical flower shape |
| CN111874938A (en) * | 2020-08-04 | 2020-11-03 | 安徽乐橙信息科技有限公司 | Preparation method of magnesium-copper hydroxy sulfate nano flower-like material |
| CN112374508A (en) * | 2020-11-02 | 2021-02-19 | 中山大学 | Amorphous nickel borate nanosheet and preparation method and application thereof |
| CN115020518A (en) * | 2022-06-10 | 2022-09-06 | 哈尔滨工业大学 | Infrared photoelectric detector based on bismuth-oxygen-sulfur micro-flower array or bismuth-oxygen-sulfur nanoflower and preparation method thereof |
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| CN1872703A (en) * | 2006-06-13 | 2006-12-06 | 中国科学院上海硅酸盐研究所 | Method for preparing Nano material of hydrate through hydrolyzing acetate |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232076A (en) * | 2013-05-16 | 2013-08-07 | 漳州师范学院 | Synthesis method of cobalt hydroxide with different grain diameters |
| CN104001523A (en) * | 2014-06-06 | 2014-08-27 | 安徽师范大学 | Cobalt/noble metal/cobalt hydroxide nano-composite material, and preparation method and application thereof |
| CN104671293A (en) * | 2015-02-02 | 2015-06-03 | 浙江大学 | Hierarchically layered monometal hydroxide as well as synthesis method and application thereof |
| KR101794454B1 (en) | 2016-07-18 | 2017-11-07 | 동국대학교 산학협력단 | Method of manufacturing a cobalt having a hierarchical flower shape |
| CN106711432A (en) * | 2016-12-21 | 2017-05-24 | 中南大学 | MoO2 nano material with three-dimensional network structure and preparation and application thereof |
| CN106711432B (en) * | 2016-12-21 | 2019-04-05 | 中南大学 | A kind of tridimensional network MoO2Nano material and its preparation and application |
| CN111874938A (en) * | 2020-08-04 | 2020-11-03 | 安徽乐橙信息科技有限公司 | Preparation method of magnesium-copper hydroxy sulfate nano flower-like material |
| CN112374508A (en) * | 2020-11-02 | 2021-02-19 | 中山大学 | Amorphous nickel borate nanosheet and preparation method and application thereof |
| CN115020518A (en) * | 2022-06-10 | 2022-09-06 | 哈尔滨工业大学 | Infrared photoelectric detector based on bismuth-oxygen-sulfur micro-flower array or bismuth-oxygen-sulfur nanoflower and preparation method thereof |
| CN115020518B (en) * | 2022-06-10 | 2023-07-11 | 哈尔滨工业大学 | Infrared photoelectric detector based on bismuth oxysulfide micro-flower array or bismuth oxysulfide nano-flower and preparation method thereof |
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