CN102807255B - 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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- CN102807255B CN102807255B CN201110144822.3A CN201110144822A CN102807255B CN 102807255 B CN102807255 B CN 102807255B CN 201110144822 A CN201110144822 A CN 201110144822A CN 102807255 B CN102807255 B CN 102807255B
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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 a synthetic focus of material by self assembly multidimensional structure material, morphology control is a key issue of current 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, the fields such as electrochemistry and vapor phase sensor have a wide range of applications, and have caused people's interest widely.The pattern of cobaltous hydroxide has important impact to its performance and application.The pattern of cobaltous hydroxide obtains a large amount of research, has successfully synthesized the one-dimentional structures such as nanometer sheet, nano wire, nanometer rod, nanotube.But three bit architecture reports are little.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 is also the one challenge during material synthesizes.The present invention is intended to utilize soft template effect, in profit two-phase system, controls pattern and the size of material, synthetic cobaltous hydroxide nano flower multidimensional structure.The present invention has no document and patent report.
Summary of the invention
In recent years, the pattern of cobaltous hydroxide obtains a large amount of research, has successfully synthesized the one-dimentional structures such as nanometer sheet, nano wire, nanometer rod, nanotube.But three-dimensional structure report is little, and these multidimensional structures all in microscopic dimensions size more than several microns, self-assembly form a micron once cobaltous hydroxide multidimensional structure rarely have report.The object of this invention is to provide a kind of cobaltous hydroxide nano flower 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 oil phase, slowly in cobalt microemulsion, drips alkali, contact is abundant, precipitation from homogeneous solution.Tensio-active agent also plays the effect of soft template, utilize its guide effect and package action, control pattern and the size of material, the one-dimentional structure cobaltous hydroxide nanometer sheet generating is assembled into the nano flower material of three-dimensional structure under soft template guide effect, simultaneously under the physically encapsulation effect of soft template, the agglomeration of limiting material, controls scantling at Nano grade.Soft template used is linear alkylbenzene sulphonic acid or the α-sodium olefin sulfonate in anion surfactant, or be Np series or the tween series of surfactants in nonionogenic tenside, or be the hexadecyl trimethyl ammonium bromide in cats product.
For achieving the above object, the technical solution used in the present invention is:
In the presence of soft template, synthetic by the method for self-assembly; Under room temperature in profit two-phase system, cobalt metal with alkali uniform contact, react, utilize the guide effect of soft template and package action to prepare.
Can operate as follows:
1) inorganic salt and precipitation agent high dispersive in oil phase: tensio-active agent, cosurfactant and organic phase are mixed to composition reverse micro emulsion A; The aqueous solution of metal soluble salt and inorganic base aqueous solution are joined respectively to the profit two-phase system B and the C that in A, obtain respectively high dispersive; It is solution D that organic amine is dissolved in organic phase.
2) precipitation from homogeneous solution: in the time using mineral alkali, under agitation condition, C is slowly added drop-wise in B, stirs 1-24h; In the time being alkali with organic amine, D is slowly added drop-wise in B, stir 1-24h.
3) material cleans: centrifugal collection solid; By washing with alcohol 2-time, remove tensio-active agent, 50-150 ℃ of oven dry, finally obtains green cobaltous hydroxide nano flower material;
The mass ratio of the final mixing solutions of gained 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.
In described cobaltous hydroxide nano flower material preparation method, chlorate, acetate, nitrate, vitriol that described metal soluble salt is metal; Described organic phase is hexanaphthene, normal hexane or toluene; Cosurfactant is propyl carbinol, Pentyl alcohol, n-hexyl alcohol or n-Octanol.Described alkali is mineral alkali, as ammoniacal liquor, and sodium hydroxide and organic bases, as organic amine, organic amine can be an alkylamine, dialkylamine and trialkylamine.
Tool of the present invention has the following advantages:
A kind of nanoflakes and cobalt hydroxide material with floriform appearance, to pile up by cobaltous hydroxide nanometer sheet the three-dimensional structure forming, the three-dimensional structure that this gathering forms presents floriform appearance, forms nano flower, and nano flower particle diameter is 300-500nm nanometer (seeing Fig. 2 and Fig. 3).This synthetic method is done simple, easily controls.There is higher specific surface area and pore volume, therefore at battery, in the fields such as catalysis, there is potential application.
Accompanying drawing explanation
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 to composition solution A; The aqueous solution of metal soluble salt and inorganic base aqueous solution are joined respectively to the profit two-phase system B and the C that in A, obtain respectively high dispersive; It is solution D that organic amine is dissolved in organic phase.In the time using inorganic base aqueous solution, under agitation condition, C is slowly added drop-wise in B, stir 1-24h.In the time being alkali with organic amine, D is slowly added drop-wise in B, stir 1-24h.Centrifugal collection solid, removes tensio-active agent with 2-6 this solid of washing of ethanol, and 80-150 ℃ of oven dry, finally obtains green cobaltous hydroxide nano flower material; The mass ratio of the final mixing solutions of gained 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.
Below by embodiment, method provided by the invention is described in detail, but do not limit in any form the present invention.
The preparation of embodiment 1 materials A
Get 5g Np-12,5g hexanaphthene and 3g n-Octanol and be mixed to get solution A; 1g Cobaltous diacetate is dissolved in 3g deionized water, adds and in A, obtains two system B of profit, and 1g ammoniacal liquor (25-28%) is dissolved in 2g water and adds in A and obtain two system C of profit, under stirring, solution C is slowly splashed into B, aging 2h; Then, the centrifugal solid that obtains; In this solid, add 30mL ethanol, heated and stirred 10min is centrifugal; Repeat this step repeatedly, until removal of surfactant is clean; Dry to obtain final nano material for 80 ℃.The Nomenclature Composition and Structure of Complexes of materials A proves α-Co (OH) by powder x-ray diffraction (XRD)
2pure phase (Fig. 1).From transmission electron microscope picture (Fig. 2) and scanning electron microscope (Fig. 3), can find out, cobaltous hydroxide multidimensional structure, is assembled and is formed by cobaltous hydroxide nanometer sheet, and whole aggregate presents floriform appearance, and about 300-500nm is better dispersed.
The preparation of embodiment 2 material B
Get 1g Sodium dodecylbenzene sulfonate, 6g toluene, 2g n-hexyl alcohol and be mixed to get solution A; 1g Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES is dissolved in 2g deionized water obtaining solution B, adds and in A, obtains two system B of profit, and add 0.03g sodium hydroxide to be dissolved in 2g water to add in A and obtain two system C of profit, under stirring, solution C is slowly splashed in B to aging 10h; Then, the centrifugal solid that obtains; In this solid, add 30ml ethanol, heated and stirred 10min is centrifugal; Repeat this step repeatedly, until removal of surfactant is clean; Dry to obtain final nano material for 80 ℃.
The preparation of embodiment 3 material C
Get 4g hexadecyl trimethyl ammonium bromide, 12g normal hexane, 4g n-hexyl alcohol and be mixed to get solution A; 1g cobalt chloride is dissolved in 3g deionized water obtaining solution B; Add in A and obtain two system B of profit, 0.4g n-Butyl Amine 99 is dissolved in 3g normal hexane and obtains solution D.Under stirring, solution D is slowly splashed in B to aging 1h; Then, the centrifugal solid that obtains; In this solid, add 30ml ethanol, heated and stirred 10min is centrifugal; Repeat this step repeatedly, until removal of surfactant is clean; Dry to obtain final nano material for 80 ℃.
The preparation of embodiment 4 material D
Get 10g tween-80,12g normal hexane, 4g Pentyl alcohol and be mixed to get solution A; 1g rose vitriol is dissolved in 3g deionized water obtaining solution B; Add in A and obtain two system B of profit, 1.4g Tributylamine is dissolved in 6g normal hexane and obtains solution D.Under stirring, solution D is slowly splashed in B to aging 2h; Then, the centrifugal solid that obtains; In this solid, add 30ml ethanol, heated and stirred 10min is centrifugal; Repeat this step repeatedly, until removal of surfactant is clean; Dry to obtain final nano material for 80 ℃.
The nanostructure of these nano particles and pattern can pass through powder x-ray diffraction (XRD), the means such as scanning electron microscope (SEM) and projection Electronic Speculum (TEM) prove, from Electronic Speculum figure, can find out, cobaltous hydroxide multidimensional structure has flower dress pattern, formed by the self-assembly of cobaltous hydroxide nanometer sheet, about 300-500nm, better dispersed.The synthetic cobaltous hydroxide nano material of the method has high specific surface area and pore volume, and in catalysis, there is potential application in the fields such as electrochemistry and vapor phase sensor.
Claims (1)
1. a preparation method with the nanoflakes and cobalt hydroxide material of floriform appearance, is characterized in that:
Be to pile up by cobaltous hydroxide nanometer sheet the three-dimensional structure forming, the three-dimensional structure that this gathering forms presents floriform appearance, forms nano flower, and nano flower particle diameter is 300-500 nm;
The multidimensional structure that described nano flower has is to be formed by the self-assembly of cobaltous hydroxide nanometer sheet;
In the presence of soft template, synthetic by the method for self-assembly; Under room temperature in profit two-phase system, cobalt metal with alkali uniform contact, react, utilize the guide effect of soft template and package action to prepare;
The preparation method of described cobaltous hydroxide material operates as follows:
1) inorganic salt and precipitation agent high dispersive in oil phase: tensio-active agent, cosurfactant and organic phase are mixed to composition solution A;
The aqueous solution of metal soluble salt is joined to the profit two-phase system B that obtains high dispersive in A;
Inorganic base aqueous solution is joined to the profit two-phase system C that obtains high dispersive in A; Or organic amine is dissolved in organic phase for solution D;
2) precipitation from homogeneous solution:
In the time using mineral alkali, under agitation condition, C is slowly added drop-wise in B, stir 1-24 h; Centrifugal collection solid;
Maybe, in the time being alkali with organic amine, D is slowly added drop-wise in B, stirs 1-24 h; Centrifugal collection solid;
3) material cleans: solid washing with alcohol 2-6 time, remove tensio-active agent, 50-150
oc is dried, and finally obtains green cobaltous hydroxide nano flower material;
In precipitation from homogeneous solution process, in final mixing solutions D+B or C+B, the mass ratio of each material is 10 tensio-active agents: 1～6 water: 5～15 organic phases: 0～6 cosurfactant: 1 metal-salt; Alkali and metal-salt mol ratio are 0.5-3.
2. according to the preparation method of the nanoflakes and cobalt hydroxide material with floriform appearance claimed in claim 1, it is characterized in that: in described preparation method, tensio-active agent is linear alkylbenzene sulphonic acid or the α-sodium olefin sulfonate in anion surfactant, or be Np series or the tween series of surfactants in nonionogenic tenside, or be the hexadecyl trimethyl ammonium bromide in cats product, it is soft template;
Described organic phase is hexanaphthene, normal hexane or toluene;
Cosurfactant is propyl carbinol, Pentyl alcohol, n-hexyl alcohol or n-Octanol.
3. according to the preparation method of the nanoflakes and cobalt hydroxide material with floriform appearance claimed in claim 1, it is characterized in that: in described preparation method, one or two or more kinds in muriate that metal soluble salt is cobalt metal, acetate, nitrate, vitriol;
Mineral alkali is ammoniacal liquor or sodium hydroxide; Organic bases is an alkylamine, dialkylamine or trialkylamine.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103232076A (en) * | 2013-05-16 | 2013-08-07 | 漳州师范学院 | Synthesis method of cobalt hydroxide with different grain diameters |
| CN104001523B (en) * | 2014-06-06 | 2017-02-15 | 安徽师范大学 | Cobalt/noble metal/cobalt hydroxide nano-composite material, and preparation method and application thereof |
| CN104671293B (en) * | 2015-02-02 | 2016-05-11 | 浙江大学 | A kind of stratiform monometallic hydroxide and synthetic method and application with hierarchical organization |
| KR101794454B1 (en) | 2016-07-18 | 2017-11-07 | 동국대학교 산학협력단 | Method of manufacturing a cobalt having a hierarchical flower shape |
| 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 |
| CN112374508B (en) * | 2020-11-02 | 2022-07-12 | 中山大学 | Amorphous nickel borate nanosheet and preparation method and application 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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| 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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| 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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| A room temperature solution-phase process to synthesize pure phase single-crystalline hexagonal cobalt hydroxide nanoplates;Wenzhong Z. Wang, et al.;《Journal of Crystal Growth》;20100916;第312卷;第3486页 * |
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