CN1712157A - Cobalt nanometer particle or crumb and production thereof - Google Patents
Cobalt nanometer particle or crumb and production thereof Download PDFInfo
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- CN1712157A CN1712157A CN 200510020660 CN200510020660A CN1712157A CN 1712157 A CN1712157 A CN 1712157A CN 200510020660 CN200510020660 CN 200510020660 CN 200510020660 A CN200510020660 A CN 200510020660A CN 1712157 A CN1712157 A CN 1712157A
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Abstract
A Co nanoparticle or its cluster features that it can be dissolved in water or easily separated from water. Its preparing process includes such steps as reacting between water-soluble thiol or mereapto compound and the aqueous solution of Co salt, reducing Co ions by reducing agent and gathering the Co ions to become Co nanoparticles or their cluster while forming a protecting layer formed by thiol moleculae.
Description
Technical field
The present invention relates to element preparation of granules field, iron group metal, particularly a kind of aqueous cobalt nano particle or cluster and preparation method thereof.
Background technology
The nano particle of magnetic metal such as cobalt etc. can be used to prepare high-density memory device, magnetic head or Magnetic Sensor, also can be used for designing magneto-resistive random access memories (MRAM), has a good application prospect in the BIOS of computer chip, military affairs, space flight.The cluster of cobalt plays good catalytic action in the growth of organic reaction (as hydrogenation catalyst, olefin cracking etc.) and nanotube, line.
Main high-temperature liquid-phase synthetic method and the high-temperature liquid-phase decomposition method of adopting of the liquid chemical method preparation of cobalt nanometer particle or cluster.The former is a reduction cobalt slaine under the condition of ligand solvent and sufficiently high solution temperature (200-300 ℃) and stabilizing agent existence; The latter then is the carbonyls that elevated temperature heat is decomposed transition metal under the condition that stabilizing agent exists.These two kinds of reaction temperatures that the preparation method all has relatively high expectations, not only the controllability of reaction reduces, and expends the energy; In addition, the external protection of these method gained cobalt nanometer particles or cluster is not the clear and definite monolayer of structure, therefore is unfavorable for the assembling of further structure or device.Eur.Phys.J.B 31 (2003) reported G.Carotenutol etc. with alkyl hydrosulfide as stabilizing agent, made the nano structural material that is inlaid with the cobalt sulfide particle by the high-temperature liquid-phase synthetic method, but they do not obtain cobalt nanometer particle or the cluster that can separate.J.Chem.Soc.; Chem.Commun. reported preparation organism single layer protecting metal-group (the MonolayerProtected Clusters that Brust proposes in nineteen ninety-five; MPC) method; this method is to react in room temperature or ice-water bath; the golden MPC particle diameter that obtains can be controlled, and can distinguish water-soluble or non-polar organic solvent according to the structure difference of outer protective layer.This golden MPC can separate from solvent (also can be described as dispersant) at an easy rate, and dissolving (or being called dispersion) and separation can not cause the gathering of particle repeatedly.Adopt the method for Brust to prepare the MPC of gold, silver, iron/platinum alloy etc., but do not find as yet to adopt similar approach to prepare the report of cobalt nanometer particle or cluster.
(notification number is 1261565 to Chinese patent database, applying date 1999.01.21) disclosing the application people is that China Science ﹠ Technology University, name are called the patent application document of " preparation method of a kind of nanometre metal cobalt powder or nickel powder ", being characterized in cobalt salt or nickel salt weight 2-5 NaOH is doubly joined in the solution of cobalt or the hydrazine hydrate of nickel ion mole more than 3 times, again with cobalt salt or nickel salt. alcohol-water solution mixes.Its weak point is that the nano particle that produces can very fast gathering, and nano particle can not stable existence.
Summary of the invention
The purpose of this invention is to provide a kind of aqueous cobalt nano particle or cluster, another object of the present invention provides the preparation method of a kind of aqueous cobalt nano particle or cluster.
Aqueous cobalt nano particle of the present invention or cluster, the composition of raw materials of this nano particle or cluster is made of following component in molar ratio:
1 part～10 parts of water soluble cobaltous salts
0.5 part～150 parts of water-soluble sulfur alcohol compounds (or claiming sulfhydryl compound)
3 parts～200 parts of reducing agents
In said components, after being dissolved in the water, water soluble cobaltous salt can produce cobalt ions, and cobalt ions is reduced into the simple substance state through reducing agent, forms cobalt nanometer particle or cluster; Simultaneously, water-soluble sulfur alcohol compound (or claiming sulfhydryl compound) then plays protectant effect, becomes one deck monolayer in the cobalt nanometer particle or the cluster surface-assembled that generate, forms stable water-soluble alkanethiol monolayer protection cobalt nanometer particle or cluster.Water-soluble sulfur alcohol compound also can contain various functional groups, makes the cobalt nanometer particle or the cluster that obtain can carry out next step reaction or have the functionalization characteristics.The said ratio scope of the combination of these components and each component; determine that by a large amount of tests combinations thereof and ratio range make cobalt nanometer particle of the present invention or cluster have above-mentioned unimolecule protective layer, can disperse lock out operation repeatedly in water, help carrying out characteristics such as the assembling of nanostructured or device or self assembly.
In the above-mentioned raw materials prescription, the content of water-soluble mercaptan is preferably 5 parts～100 parts, and reducing agent is preferably 5～100 parts.In preferable range, reaction yield is higher, and the reaction controllability is good.
In the composition of raw materials of the present invention, water soluble cobaltous salt is meant the cobalt salt that can be dissolved in water, they can be that the cobalt salt of divalence also can be the cobalt salt of trivalent, and water soluble cobaltous salt can adopt cobaltous sulfate, cobalt nitrate, cobalt acetate, cobalt chloride etc., wherein cobaltous sulfate preferably.Water-soluble sulfur alcohol compound adopts the single sulfur alcohol compound that contains a sulfydryl, as succinic acid mercaptan, Tiopronin, L-cysteine and composition thereof or substituent etc., and wherein preferably succinic acid mercaptan and Tiopronin.Reducing agent can be used trisodium citrate, sodium borohydride, ascorbic acid, white phosphorus, hydrazine, azanol etc., wherein sodium borohydride preferably.
The method for preparing cobalt nanometer particle of the present invention or cluster is made up of following steps successively:
(a) ratio in above-mentioned prescription is dissolved in the water water soluble cobaltous salt and sulfur alcohol compound protective agent respectively, forms the aqueous solution;
(b) under room temperature or low temperature, the sulfur alcohol compound aqueous solution and cobalt saline solution are mixed, and under this temperature, continue stirring reaction 0.5 hour～10 hours;
(c) reducing agent is dissolved in the water, and the mixed system of sulfur alcohol compound and cobalt salt is placed ice-water bath;
(d) the reducing agent aqueous solution is added in the reaction system of sulfur alcohol compound and cobalt salt, stirring reaction is 0.5 hour～10 hours in ice-water bath;
(e) after reaction finishes, the insoluble matter in the system is removed by filter, promptly obtain the cobalt nanometer particle of sulfur alcohol compound protection or the aqueous solution (or being called aqueous dispersions) of cluster;
(f) remove excessive sulfur alcohol compound and other ion by dialysis process, obtain the cobalt nanometer particle of pure sulfur alcohol compound protection or the aqueous solution of cluster;
(g) under 40 ℃, after rotary evaporation and vacuum drying, obtain the cobalt nanometer particle or the cluster of solid shape sulfur alcohol compound protection.
Can remove protective agent by methods such as heating, ultrasonic technologies by cobalt nanometer particle or cluster that the solid shape sulfur alcohol compound of above method preparation is protected, obtain pure cobalt nanometer particle or cluster.
The invention provides the method that under low temperature or room temperature condition, prepares water miscible cobalt nanometer particle or cluster.Cobalt nanometer particle that makes or cluster skin have the water-soluble sulfur alcohol compound protection of monolayer, can stably be dissolved in (or claiming to be scattered in) water, can adopt conventional separation means that it is separated from water, obtain solid; After solid is soluble in water again, still can not assemble.The cobalt nanometer particle of this structure or cluster also are particularly conducive to assembling or the self assembly of carrying out nanostructured or device.Preparation method of the present invention, reaction condition is gentle, is easy to control, and product stability at normal temperatures is high.
Description of drawings
Fig. 1 is the cobalt nanometer particle under the sulfur alcohol compound single ply protective of the present invention or the structural representation of cluster
The specific embodiment
Further specify the present invention below by specific embodiment.
The cobalt nanometer particle of the sulfur alcohol compound single ply protective of gained of the present invention or the structure of cluster are as shown in Figure 1.
In Fig. 1; the sulfur alcohol compound molecule is a protective agent; because electrostatic interaction between the protective agent and the interaction between protective agent and the aqueous solvent have suppressed the gathering of metal nanoparticle or cluster, thereby have obtained the cobalt nanometer particle or the cluster of the sulfur alcohol compound single ply protective of stable existence in water.
Embodiment 1
Earlier 1 part of cobaltous sulfate and 3 parts of succinic acid mercaptan are dissolved in respectively in distilled water or the deionized water, the succinic acid mercaptan aqueous solution are added in the cobalt sulfate solution again, reaction is 30 minutes under ice-water bath and stirring.The aqueous solution of 5 parts of borane reducing agent sodium hydrides is added reaction system, and continue under ice-water bath and stirring, to react 30 minutes, obtain pitchy or purplish cobalt nanometer particle or the cluster aqueous solution.Can obtain the cobalt nanometer particle or the cluster solid of pure, stable succinic acid mercaptan protection after this aqueous solution process filtration, dialysis, the drying.
Embodiment 2
Earlier 5 parts of cobaltous sulfates and 50 parts of Tiopronins are dissolved in respectively in distilled water or the deionized water, the Tiopronin aqueous solution are added in the cobalt sulfate solution again, reaction is 60 minutes under ice-water bath and stirring.The aqueous solution of 40 parts of borane reducing agent sodium hydrides is added reaction system, and continue under ice-water bath and stirring, to react 80 minutes, obtain pitchy or purplish cobalt nanometer particle or the cluster aqueous solution.Can obtain the cobalt nanometer particle or the cluster solid of pure, stable Tiopronin protection after this aqueous solution process filtration, dialysis, the drying.
Embodiment 3
Earlier 10 parts of cobaltous sulfates and 150 parts of succinic acid mercaptan are dissolved in respectively in distilled water or the deionized water, the succinic acid mercaptan aqueous solution are added in the cobalt sulfate solution again, reaction is 480 minutes under ice-water bath and stirring.The aqueous solution of 200 parts of borane reducing agent sodium hydrides is added reaction system, and continue under ice-water bath and stirring, to react 380 minutes, obtain pitchy or purplish cobalt nanometer particle or the cluster aqueous solution.Can obtain the cobalt nanometer particle or the cluster solid of pure, stable succinic acid mercaptan protection after this aqueous solution process filtration, dialysis, the drying.
Embodiment 4
Earlier 1 part of cobalt acetate and 3 parts of succinic acid mercaptan are dissolved in respectively in distilled water or the deionized water, the succinic acid mercaptan aqueous solution are added in the cobalt acetate aqueous solution again, reaction is 30 minutes under ice-water bath and stirring.The aqueous solution of 5 parts of reducing agent ascorbic acid is added reaction system, and continue under ice-water bath and stirring, to react 30 minutes, obtain pitchy or purplish cobalt nanometer particle or the cluster aqueous solution.Can obtain the cobalt nanometer particle or the cluster solid of pure, stable succinic acid mercaptan protection after this aqueous solution process filtration, dialysis, the drying.
Embodiment 5
Earlier 5 parts of cobalt acetates and 50 parts of Tiopronins are dissolved in respectively in distilled water or the deionized water, the Tiopronin aqueous solution are added in the cobalt acetate aqueous solution again, reaction is 60 minutes under ice-water bath and stirring.The aqueous solution of 100 parts of borane reducing agent sodium hydrides is added reaction system, and continue under ice-water bath and stirring, to react 80 minutes, obtain pitchy or purplish cobalt nanometer particle or the cluster aqueous solution.Can obtain the cobalt nanometer particle or the cluster solid of pure, stable Tiopronin protection after this aqueous solution process filtration, dialysis, the drying.
Embodiment 6
Earlier 10 parts of cobalt acetates and 150 parts of succinic acid mercaptan are dissolved in respectively in distilled water or the deionized water, the succinic acid mercaptan aqueous solution are added in the cobalt acetate aqueous solution again, reaction is 450 minutes under ice-water bath and stirring.The aqueous solution of 80 parts of borane reducing agent sodium hydrides is added reaction system, and continue under ice-water bath and stirring, to react 300 minutes, obtain pitchy or purplish cobalt nanometer particle or the cluster aqueous solution.Can obtain the cobalt nanometer particle or the cluster solid of pure, stable succinic acid mercaptan protection after this aqueous solution process filtration, dialysis, the drying.
Embodiment 7
Earlier 1 part of cobalt chloride and 10 parts of succinic acid mercaptan are dissolved in respectively in distilled water or the deionized water, the succinic acid mercaptan aqueous solution are added in the cobalt chloride solution again, reaction is 60 minutes under ice-water bath and stirring.The aqueous solution of 8 parts of reducing agent trisodium citrates is added reaction system, and continue under ice-water bath and stirring, to react 50 minutes, obtain pitchy or purplish cobalt nanometer particle or the cluster aqueous solution.Can obtain the cobalt nanometer particle or the cluster solid of pure, stable succinic acid mercaptan protection after this aqueous solution process filtration, dialysis, the drying.
Embodiment 8
Earlier 1 part of cobalt nitrate and 3 parts of succinic acid mercaptan are dissolved in respectively in distilled water or the deionized water, the succinic acid mercaptan aqueous solution are added in the cobalt acetate aqueous solution again, reaction is 30 minutes under ice-water bath and stirring.The aqueous solution of 5 parts of reducing agent trisodium citrates is added reaction system, and continue under ice-water bath and stirring, to react 30 minutes, obtain pitchy or purplish cobalt nanometer particle or the cluster aqueous solution.Can obtain the cobalt nanometer particle or the cluster solid of pure, stable succinic acid mercaptan protection after this aqueous solution process filtration, dialysis, the drying.
Embodiment 9
Earlier 5 parts of cobalt acetates and 40 parts of Tiopronins and 5 parts of L-cysteines are dissolved in respectively in distilled water or the deionized water, the Tiopronin aqueous solution are added in the cobalt acetate aqueous solution again, reaction is 60 minutes under ice-water bath and stirring.The aqueous solution of 100 parts of borane reducing agent sodium hydrides is added reaction system, and continue under ice-water bath and stirring, to react 80 minutes, obtain pitchy or purplish cobalt nanometer particle or the cluster aqueous solution.Can obtain the cobalt nanometer particle or the cluster solid of pure, stable Tiopronin and the protection of L-cysteine after this aqueous solution process filtration, dialysis, the drying.
Embodiment 10
Earlier 10 parts of cobalt acetates and 150 parts of succinic acid mercaptan are dissolved in respectively in distilled water or the deionized water, the succinic acid mercaptan aqueous solution are added in the cobalt acetate aqueous solution again, reaction is 400 minutes under ice-water bath and stirring.The aqueous solution of 80 parts of reducing agent tetramethyl azanols is added reaction system, and continue under ice-water bath and stirring, to react 200 minutes, obtain pitchy or purplish cobalt nanometer particle or the cluster aqueous solution.Can obtain the cobalt nanometer particle or the cluster solid of pure, stable succinic acid mercaptan protection after this aqueous solution process filtration, dialysis, the drying.
Embodiment 11
Earlier 1 part of cobalt chloride and 10 parts of succinic acid mercaptan are dissolved in respectively in distilled water or the deionized water, the succinic acid mercaptan aqueous solution are added in the cobalt chloride solution again, reaction is 60 minutes under ice-water bath and stirring.The aqueous solution of 8 parts of borane reducing agent sodium hydrides is added reaction system, and continue under ice-water bath and stirring, to react 50 minutes, obtain pitchy or purplish cobalt nanometer particle or the cluster aqueous solution.Can obtain the cobalt nanometer particle or the cluster solid of pure, stable succinic acid mercaptan protection after this aqueous solution process filtration, dialysis, the drying.
Claims (10)
1. cobalt nanometer particle or cluster, the composition of raw materials that it is characterized in that this nano particle or cluster is counted component in molar ratio and is:
1 part～10 parts of water soluble cobaltous salts
0.5 part～150 parts of water-soluble sulfur alcohol compounds
3 parts～200 parts of reducing agents
2. cobalt nanometer particle according to claim 1 or cluster, water soluble cobaltous salt wherein are the cobalt salt of divalence or the cobalt salt of trivalent.
3. cobalt nanometer particle according to claim 2 or cluster, water soluble cobaltous salt wherein are a kind of or its mixture in cobaltous sulfate, cobalt nitrate, cobalt acetate, the cobalt chloride.
4. cobalt nanometer particle according to claim 3 or cluster, water soluble cobaltous salt wherein is a cobaltous sulfate.
5. according to arbitrary described cobalt nanometer particle of claim 1～4 or cluster, water-soluble sulfur alcohol compound wherein is a kind of or its mixture and the substituent in succinic acid mercaptan, L-cysteine, the Tiopronin.
6. cobalt nanometer particle according to claim 5 or cluster, wherein water-soluble mercaptans content are 5 parts～100 parts.
7. according to arbitrary described cobalt nanometer particle of claim 1～6 or cluster, reducing agent is a kind of in trisodium citrate, sodium borohydride, ascorbic acid, white phosphorus, hydrazine, the azanol.
8. according to arbitrary described cobalt nanometer particle of claim 7 or cluster, reducing agent wherein is a sodium borohydride.
9. according to arbitrary described cobalt nanometer particle of claim 1～8 or cluster, wherein reducing agent content is 5 parts～100 parts.
10. the method for preparing described cobalt nanometer particle of claim 1 or cluster is characterized in that this method may further comprise the steps:
(a) water soluble cobaltous salt and sulfur alcohol compound protective agent are dissolved in the water respectively, form the aqueous solution;
(b) under room temperature or low temperature, the sulfur alcohol compound aqueous solution and cobalt saline solution are mixed, and under this temperature, continue stirring reaction 0.5～10 hour;
(c) reducing agent is dissolved in the water, and the mixed system of sulfur alcohol compound and cobalt salt is placed ice-water bath;
(d) the reducing agent aqueous solution is added in the reaction system of sulfur alcohol compound and cobalt salt, stirring reaction is 0.5～10 hour in ice-water bath;
(e) insoluble matter in the system is filtered away, promptly obtain the cobalt nanometer particle of sulfur alcohol compound protection or the aqueous solution of cluster;
(f) remove excessive mercaptan plasma by dialysis process, obtain the cobalt nanometer particle of pure sulfur alcohol compound protection or the aqueous solution of cluster;
(g) under 40 ℃, after rotary evaporation and vacuum drying, obtain the cobalt nanometer particle or the cluster of solid shape sulfur alcohol compound protection.
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| CNB2005100206607A CN100534674C (en) | 2005-03-31 | 2005-03-31 | Cobalt nanometer particle or crumb and production thereof |
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| CNB2005100206607A CN100534674C (en) | 2005-03-31 | 2005-03-31 | Cobalt nanometer particle or crumb and production thereof |
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| CN1712157A true CN1712157A (en) | 2005-12-28 |
| CN100534674C CN100534674C (en) | 2009-09-02 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008098830A1 (en) * | 2007-02-14 | 2008-08-21 | Evonik Degussa Gmbh | Noble metal catalysts |
| CN101698234B (en) * | 2009-10-21 | 2011-02-16 | 北京科技大学 | Chemical preparation method of metal cobalt nanowire |
| CN102921960A (en) * | 2012-11-19 | 2013-02-13 | 扬州大学 | Preparation method of magnetic cobalt nanometer material |
| CN103990810A (en) * | 2014-05-30 | 2014-08-20 | 洛阳理工学院 | Technology for preparing nanometer indium powder |
| CN104174863A (en) * | 2013-05-21 | 2014-12-03 | 国家纳米科学中心 | Germanium nano cluster and preparation method and application thereof |
| CN108145173A (en) * | 2016-12-04 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of preparation method of the controllable palladium nano-cluster of size |
-
2005
- 2005-03-31 CN CNB2005100206607A patent/CN100534674C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008098830A1 (en) * | 2007-02-14 | 2008-08-21 | Evonik Degussa Gmbh | Noble metal catalysts |
| CN101698234B (en) * | 2009-10-21 | 2011-02-16 | 北京科技大学 | Chemical preparation method of metal cobalt nanowire |
| CN102921960A (en) * | 2012-11-19 | 2013-02-13 | 扬州大学 | Preparation method of magnetic cobalt nanometer material |
| CN104174863A (en) * | 2013-05-21 | 2014-12-03 | 国家纳米科学中心 | Germanium nano cluster and preparation method and application thereof |
| CN104174863B (en) * | 2013-05-21 | 2016-08-10 | 国家纳米科学中心 | A kind of germanium nanocluster, Its Preparation Method And Use |
| CN103990810A (en) * | 2014-05-30 | 2014-08-20 | 洛阳理工学院 | Technology for preparing nanometer indium powder |
| CN108145173A (en) * | 2016-12-04 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of preparation method of the controllable palladium nano-cluster of size |
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| CN100534674C (en) | 2009-09-02 |
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