CN102554217A - Water-soluble nano-copper and preparation method thereof - Google Patents
Water-soluble nano-copper and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of nanometer materials, and particularly relates to water-soluble nano-copper and a preparation method of the water-soluble nano-copper, wherein the water-soluble nano-copper is nano-copper clusters which are surface-modified by stable organic single molecules formed in a way that organic compound surface modifier containing sulfydryl is bonded on the surface of copper nanoparticles. The invention can obtain copper nanoparticles which can be effectively dispersed in water phases and can exist stably, and is simple in preparation process and preparation devices, low in raw material cost, low in the production cost, high in yield, and suitable for large-scale industrial production, and the raw materials are easily accessible.
Description
Technical field
The invention belongs to technical field of nano material, particularly a kind of water-soluble nano copper and preparation method thereof.
Background technology
Nanometer copper because of its special physicochemical properties are widely used in fields such as electrically-conducting paint, electrode material, magnetic fluid, catalysis, has especially shown the application prospect that it is wide as the novel lubricating material as an important branch of metal nano material.But the specific area of pure nano-copper particle is big, and chemism is high, and is very easily oxidized and lose original physicochemical characteristics in air, and the bad dispersibility in medium, is easy to generate deposition.The defective of nano copper particle stability and bad dispersibility has greatly limited its application in industrial circle, therefore need carry out finishing to nanometer copper.
The research of preparation, performance and the application of relevant surface finish nano copper particulate in recent years at home and abroad receives widely always to be paid close attention to.The in-situ surface finishing technology is when nanoparticle forms, and dressing agent coats nanoparticle, can control the reunion and the raising of nano particle effectively and improve its dispersed and stable in medium.Wherein the nanometer copper of the monolayer of in-situ surface finishing protection is rolled into a ball bunch (Monolayer-Protected Cluster Molecules; Abbreviation Cu MPC) is different from the nanometer copper particulate that utilizes prepared by other; They normally utilize the organic molecule that extremely strong affinity is arranged with metallic copper as part, and nano copper particle and organic ligand form supramolecular system through the assembled in forms of covalency or coordination.These MPC have advantages of higher stability usually, can from solvent, separate and disperse advantages such as easy preparation repeatedly.
At present, the preparation of the nanometer copper group that the organic supramolecular layer is modified bunch mainly concentrates on oil-soluble nanometer copper (organosol of copper) aspect, and the research of water-soluble nano copper (hydrosol of copper) is less.For example, He'nan University opens people such as the bright eighteenth of the twenty and has invented employing in-situ surface finishing technology, has prepared oil solubility nanometer copper (organosol) (publication number CN 101259531A) through the liquid phase chemical reduction method.And tested nanometer copper and had good extreme-pressure anti-wear effect and good antioxygenic property, realized suitability for industrialized production, but its application can only be confined in the apolar medium as lube oil additive.People such as O.Tzhayik have prepared the nanometer copper hydrosol with xanthic derivative as dressing agent, but its stabilization time is shorter, is easy to generate deposition; See O.Tzhayik.etal., Langmuir., (2002) 18:3364.The existing nanometer copper organosol and the hydrosol be because of can not be water-soluble or poor stability in water, with water as the commercial Application of medium in like aqueous cutting fluid and water catalysis in, be difficult to bring into play the lubricated and catalytic performance of its due excellence.Consider that from environmental friendliness and economic angle the research and development of water-base nano copper are a kind of development trends simultaneously, therefore develop and to have important significance for theories and practical value at the nanometer copper particulate of effective dispersion of aqueous phase and stable existence.
Summary of the invention
The object of the present invention is to provide a kind of water-soluble nano copper and preparation method thereof, the nanometer copper of acquisition can form the metal nano copper particulate of stable dispersion at stable existence under the usual conditions, in water with the form of " dissolving ".
The technical scheme that the present invention adopts is following:
A kind of water-soluble nano copper, described nanometer copper are the nanometer copper group bunch that contains the stable organic supramolecular finishing that surface that sulfydryl organic compound coating material is bonded to the metallic copper nanoparticle forms, and structural formula is following:
Wherein R is the straight or branched alkyl, X is-OH ,-NH
2,-COOH ,-SO
3H ,-SH functional group or its salt, R institute carbon atoms number is 1-5,700≤m≤5500,175≤n≤5500.
The present invention also further provides a kind of preparation method of water-soluble nano copper; Preparation earlier contains the mixed-alkali solution of reducing agent, coating material; Then the copper precursor solution is joined in the above-mentioned mixed solution; Be reaction 0.5-10 h under the alkali condition of 9-14 at pH, promptly get said water-soluble nano copper.
The amount of substance ratio that feeds intake of copper precursor, reducing agent, coating material is 1:0.1-10:0.1-10.
The presoma of copper is one or more the mixture in copper sulphate, copper chloride, copper nitrate, Schweinfurt green, the Kocide SD.
The concentration of copper precursor solution is 0.1-1 mol/L.
Described reducing agent is one or more the mixture in formaldehyde, sodium borohydride, sodium hypophosphite, hydrazine hydrate, the ascorbic acid.
Reductant solution concentration is 0.02-2mol/L, and the concentration of dressing agent solution is 0.02-1mol/L.
Dissolvant of reaction system is water or ethanol water.
Adopt the pH value of following one or more adjustment reaction systems: NaOH, urea, ammoniacal liquor, ethylenediamine, diethylamine or triethanolamine.
Reacting on 10-80 ℃ carries out.
Nanometer copper according to the invention is meant that coating material contains the nanometer copper group bunch (Monolayer-Protected Clusters is called for short a MPC) of the stable organic supramolecular finishing that surface that the sulfydryl organic compound is bonded to the metallic copper nanoparticle forms.
The invention provides a kind of particle diameter and the controlled nano copper particle of pattern homogeneous; Size is between 1-25 nm and be evenly distributed; Antioxygenic property and the favorable dispersibility in water; Can in water, separate repeatedly and disperse, can not produce irreversible reunion and decomposition, and this colloidal sol is through obtaining the nanometer copper products of powder form after the spray-drying.In the preparation; The present invention is from the angle of in-situ surface finishing nanoparticle and the angle of MOLECULE DESIGN viewpoint; The surface modification of metallic copper nanoparticle has been done more deep research; The result finds that finishing has sulfhydryl compound and the peripheral nano-particle of copper that is connected with the hydrophilic functional groups of polarity not only to have homogeneous particle diameter and pattern, and has good dispersiveness and stable at aqueous phase.Concrete; In the liquid-phase reduction course of reaction promptly when nano-particle of copper tentatively generates; Coating material is incorporated into the surface of nano-particle of copper through the mode of coordinate bond or other strong chemical bonds; So just changed the surface microstructure of nano-particle of copper, guaranteed that nano-particle of copper is dispersed in the medium with the form of single particulate.Stoped the generation of further growing up and reuniting of copper nano-particle so on the one hand, the coating effect of coating material has simultaneously also stoped the aerial oxidation of metallic copper nanoparticle, has improved its stability.In addition on the one hand,, can realize the designability of nano-particle of copper surface texture, reach the purpose of in particular medium (water), disperseing through changing the polarity of dressing agent and contained functional group thereof.
The novel metal nanometer copper hydrosol (powder) that obtains can be used for industrial circles such as water based additive for metal machining liquid, water base lubricant, the processing of microcircuit plate, pottery processing, catalyst.
The present invention has following advantage with respect to prior art:
The present invention can obtain can be at the nanometer copper particulate of effective dispersion of aqueous phase and stable existence, and preparation technology and equipment are simple, and low in raw material cost is easy to get, and production cost is low, and productive rate is high, is fit to large-scale industrial production.
Description of drawings
Fig. 1 is the uv-visible absorption spectroscopy figure of the nanometer copper hydrosol (being water-soluble nano copper) of differential responses time acquisition under embodiment 1 condition; In the reaction time of abscissa representative among the figure, as can be seen from the figure, along with the increase in reaction time, the absworption peak of the nanometer copper hydrosol at 410 nm places strengthens gradually, nanometer copper particulate has been described along with the increase in reaction time, and grain size increases gradually.
Fig. 2 is the photo of the nanometer copper hydrosol that the differential responses time obtains among Fig. 1; As can be seen from the figure, along with the carrying out of reaction, the color of the nanometer copper hydrosol is gradually by the colourless yellow that changes into; The formation of this interval scale nanometer copper nucleus; Along with the increase in reaction time, its color changes redness, peony into by yellow gradually subsequently, and this shows the increase along with the reaction time; Nanometer copper particulate is through " Oswald that moral " maturing process, and nanoparticle is grown up gradually.
Fig. 3 is the HRTEM figure of the nanometer copper hydrosol of embodiment 3 acquisitions; As can be seen from the figure, the size of nanometer copper particulate is between 3-8nm, and average-size is 5nm, and the monodispersity of size is good.
Fig. 4 is the XPS figure of Cu element in the copper nanoparticle body after the nanometer copper hydrosol spray-drying that obtains of embodiment 1.As can be seen from the figure, through XPS analysis, the total copper Cu of powder sample
2p3/2Binding energy at 932.7ev, the nanometer copper that this explanation obtains is with metallic state, rather than exists with the form of its oxide.
Fig. 5 is the infrared spectrogram of the nano-particle of copper of embodiment 1 TGA and modification thereof.Can see that therefrom (curve is 2550 cm a) in the pure TGA molecule
-1Be V
S-HCharacteristic absorption peak, but disappear through this characteristic peak in the infrared spectrum of the nanometer copper (curve b) of modified, explained that TGA molecule and copper are surperficial to be connected through the S-H key.COO in addition
-Symmetrical stretching vibration peak and asymmetric stretching vibration peak respectively by 1398.8 cm
-1, 1608.9 cm
-1Red shift to 1411.7 cm
-1, 1727.4 cm
-1, explained that nanoparticle is to COO
-Molecular vibration exist tangible influence, also explained simultaneously through the nano-particle surface after modifying to exist hydrogen bond action.
Fig. 6 is the infrared spectrogram of the nano-particle of copper of embodiment 4 cysteines and modification thereof.Visible by figure, (curve is 2550 cm a) in the pure cysteine molecule
-1Be V
S-HCharacteristic absorption peak, but disappear through this characteristic peak in the infrared spectrum of the nanometer copper (curve b) of modified, explained that cysteine molecule and copper are surperficial to be connected through the S-H key.Be positioned at the N-H vibration peak in addition by 2985.4 cm
-1, 3178.1 cm
-1Red shift to 3428.3 cm
-1And COO
-Symmetrical stretching vibration peak and asymmetric stretching vibration peak by 1397.7 cm
-1, 1582.1 cm
-1Be changed to 1392.2 cm
-1, 1595.0 cm
-1, the COO of nanoparticle to cysteine has been described
-There is not tangible influence in molecular vibration.Combining Fig. 5,6 can know: the S-H key in the dressing agent molecule is destroyed; And N-H, C=O, C-O key do not destroy; Explain that TGA and cysteine are through sulfydryl and nanometer copper microparticle surfaces generation bonding; Describe consistently in this and the front nanometer steel structure formula, TGA and cysteine are successfully modified in the surface of nanometer copper, and this just nanometer copper particulate have the reason of good water-solubility.
Fig. 7 places the optical photograph after 0.5 hour, 1 day, 15 days respectively for the nanometer copper hydrosol that obtains under embodiment 4 conditions.As can be seen from the figure, along with the prolongation of standing time, change has taken place in the color of the nanometer copper hydrosol, gradually from light to dark, but does not find significantly to reunite and deposited phenomenon, explains that the nanometer copper of this method preparation has long-term good dispersion stabilization.
The specific embodiment
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
In 80 mL distilled water, add 15 mL NH successively
3H
2O, 0.016 mol TGA, 5 mL 80% (mass concentration, down together) hydrazine hydrate are transferred to them in 500 mL three-neck flasks then, are stirred to dissolving fully, and this moment, solution was water white transparency, and note is done the system I; With 0.032 mol CuSO
45H
2O puts into beaker, adds 100 mL distilled water and dissolves fully, and solution is blue, and note is done the system II; And II slowly is added drop-wise in the above-mentioned I mixed solution, 80 ℃ of constant temperature are reaction 1 h fully, obtain the dark red brown nanometer copper hydrosol at last, and this nanometer copper hydrosol can steady in a long-term the dispersion in water and do not have coagulation.
In 85 mL distilled water, add 15 mL NH successively
3H
2O, 0.016mol TGA, 0.6048 g (0.016mol) NaBH
4, then it is transferred in the 500 mL three-neck flasks, be stirred to dissolving fully, this moment, solution was water white transparency, note is done the system I; With 0.032 mol Cu (NO
3)
23H
2O puts into beaker, adds 100 mL distilled water and dissolves fully, and solution is blue, and note is done the system II; And II slowly is added drop-wise in the above-mentioned I mixed solution, 60 ℃ of constant temperature are reaction 2h fully, obtain the dark red brown nanometer copper hydrosol at last, and this nanometer copper hydrosol can steady in a long-term the dispersion in water and do not have coagulation.
Embodiment 3
In 80 mL distilled water, add 15 mL NH successively
3H
2O, 0.016 mol TGA, 5 mL, 80% hydrazine hydrate are transferred to them in 500 mL three-neck flasks then, are stirred to dissolving fully, and this moment, solution was water white transparency, and note is done the system I; With 0.032 mol Cu (OH)
2Put into beaker, add 100 mL distilled water and disperse fully, system is blue, and note is done the system II; And II slowly is added drop-wise in the above-mentioned I mixed solution, 40 ℃ of constant temperature are reaction 2 h fully, obtain the dark red brown nanometer copper hydrosol at last, and this nanometer copper hydrosol can steady in a long-term the dispersion in water and do not have coagulation.
Embodiment 4
In 19 mL distilled water, add 0.52 g NaOH, 1 mL, 80% hydrazine hydrate, 0.7754 g cysteine successively, then it is transferred in the 100 mL three-neck flasks, be stirred to dissolving fully, this moment, solution was water white transparency, note is done the system I; With 0.032 mol Cu (OH)
2Put into beaker, add 100 mL water and disperse fully, system is blue, and note is done the system II; And II slowly is added drop-wise in the above-mentioned I mixed solution, 40 ℃ of constant temperature are reaction 2 h fully, obtain the nanometer copper hydrosol of rufous at last, and this nanometer copper hydrosol can steady in a long-term the dispersion in water and do not have coagulation.
In 80 mL distilled water, add 15 mL NH successively
3H
2O, 0.005 mol sulfydryl propane sulfonic acid sodium, 5 mL80% hydrazine hydrates are transferred to them in 500 mL three-neck flasks then, are stirred to dissolving fully, and this moment, solution was water white transparency, and note is done the system I; With 0.032 mol CuSO
45H
2O puts into beaker, adds 100 mL distilled water and dissolves fully, and solution is blue, and note is done the system II; And II slowly is added drop-wise in the above-mentioned I mixed solution, 40 ℃ of constant temperature are reaction 6 h fully, obtain the dark red brown nanometer copper hydrosol at last, and this nanometer copper hydrosol can steady in a long-term the dispersion in water and do not have coagulation.
Embodiment 6
In 80 mL distilled water, add 15 mL NH successively
3H
2O, 0.005 mol mercaptoethylmaine hydrochloride, 5 mL80% hydrazine hydrates are transferred to them in 500 mL three-neck flasks then, are stirred to dissolving fully, and this moment, solution was water white transparency, and note is done the system I; With 0.032 mol CuSO
45H
2O puts into beaker, adds 100 mL distilled water and dissolves fully, and solution is blue, and note is done the system II; And II slowly is added drop-wise in the above-mentioned I mixed solution, 20 ℃ of constant temperature are reaction 6 h fully, obtain the dark red brown nanometer copper hydrosol at last, and this nanometer copper hydrosol can steady in a long-term the dispersion in water and do not have coagulation.
Embodiment 7
In 80 mL distilled water, add 15 mL triethanolamines, 0.016 mol TGA, 5 mL, 80% hydrazine hydrate successively, then it is transferred in the 500 mL three-neck flasks, be stirred to dissolving fully, this moment, solution was water white transparency, note is done the system I; With 0.032 mol Cu (OH)
2Put into beaker, add 100 mL distilled water and disperse fully, system is blue, and note is done the system II; And II slowly is added drop-wise in the above-mentioned I mixed solution, 40 ℃ of constant temperature are reaction 2 h fully, obtain the dark red brown nanometer copper hydrosol at last, and this nanometer copper hydrosol can steady in a long-term the dispersion in water and do not have coagulation.
Embodiment 8
In the mixed solution that contains 20 ml ethanol and 80 mL distilled water, add 15 mL NH successively
3H
2O, 0.016 mol TGA, 5 mL 80% (mass concentration, down together) hydrazine hydrate are transferred to them in 500 mL three-neck flasks then, are stirred to dissolving fully, and this moment, solution was water white transparency, and note is done the system I; With 0.032 mol CuCl
2Put into beaker, add 100 mL distilled water and dissolve fully, solution is blue, and note is done the system II; And II slowly is added drop-wise in the above-mentioned I mixed solution, 80 ℃ of constant temperature are reaction 1 h fully, obtain the dark red brown nanometer copper hydrosol at last, and this nanometer copper hydrosol can steady in a long-term the dispersion in water and do not have coagulation.
The foregoing description is the preferred embodiment of the present invention, but embodiment of the present invention is not restricted to the described embodiments, and other the change that any the present invention of not deviating from did all should be the substitute mode of equivalence, is included within protection scope of the present invention.
Claims (10)
1. a water-soluble nano copper is characterized in that, described nanometer copper is the nanometer copper group bunch that contains the stable organic supramolecular finishing that surface that sulfydryl organic compound coating material is bonded to the metallic copper nanoparticle forms, and structural formula is following:
Wherein R is the straight or branched alkyl, X is-OH ,-NH
2,-COOH ,-SO
3H ,-SH functional group or its salt, R institute carbon atoms number is 1-5,700≤m≤5500,175≤n≤5500.
2. the preparation method of the described water-soluble nano copper of claim 1; It is characterized in that; Preparation earlier contains the mixed-alkali solution of reducing agent, coating material; Then the copper precursor solution being joined in the above-mentioned mixed solution, is reaction 0.5-10 h under the alkali condition of 9-14 at pH, promptly gets said water-soluble nano copper.
3. the preparation method of water-soluble nano copper as claimed in claim 2 is characterized in that, the amount of substance ratio that feeds intake of copper precursor, reducing agent, coating material is 1:0.1-10:0.1-10.
4. the preparation method of water-soluble nano copper as claimed in claim 3 is characterized in that, the presoma of described copper is one or more the mixture in copper sulphate, copper chloride, copper nitrate, Schweinfurt green, the Kocide SD.
5. the preparation method of water-soluble nano copper as claimed in claim 3 is characterized in that, described reducing agent is one or more the mixture in formaldehyde, sodium borohydride, sodium hypophosphite, hydrazine hydrate, the ascorbic acid.
6. the preparation method of water-soluble nano copper as claimed in claim 3 is characterized in that, dissolvant of reaction system is water or ethanol water.
7. the preparation method of water-soluble nano copper as claimed in claim 3 is characterized in that, the concentration of copper precursor solution is 0.1-1 mol/L.
8. the preparation method of water-soluble nano copper as claimed in claim 3 is characterized in that, the concentration of the reducing agent of preparation and the solution of coating material is respectively 0.02-2mol/L and 0.02-1mol/L.
9. the preparation method of water-soluble nano copper as claimed in claim 3 is characterized in that, the pH value of reaction system adopts one or more adjustment in NaOH, urea, ammoniacal liquor, ethylenediamine, diethylamine or the triethanolamine.
10. like the preparation method of the described water-soluble nano copper of one of claim 2-9, it is characterized in that, react on 10-80 ℃ and carry out.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1354056A (en) * | 2001-10-12 | 2002-06-19 | 中国科学院兰州化学物理研究所 | Metal copper nano granules, its preparation method and application |
| CN101049918A (en) * | 2007-05-11 | 2007-10-10 | 北京化工大学 | Method for preparing CdTe Nano grains possible to be dissolved in water and organic solvent |
| CN101077527A (en) * | 2006-05-26 | 2007-11-28 | 中国科学院兰州化学物理研究所 | Method for preparing cuprum nickle duplex metal nano granule |
| CN101161377A (en) * | 2006-10-11 | 2008-04-16 | 三星电机株式会社 | Methods for surface modification of non-dispersible metal nanoparticles and modified metal nanoparticles for inkjet by the same method |
| KR20080057407A (en) * | 2006-12-20 | 2008-06-25 | 주식회사 포스코 | Method of surface treatment of metal particle using self assembly, metal particle thereby, making method of polymer solution containing the metal particle and coating steel panel thereby |
| CN101259531A (en) * | 2008-03-31 | 2008-09-10 | 河南大学 | Surface finish nano copper/copper alloy particles and preparation thereof |
-
2012
- 2012-02-24 CN CN201210043341.8A patent/CN102554217B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1354056A (en) * | 2001-10-12 | 2002-06-19 | 中国科学院兰州化学物理研究所 | Metal copper nano granules, its preparation method and application |
| CN101077527A (en) * | 2006-05-26 | 2007-11-28 | 中国科学院兰州化学物理研究所 | Method for preparing cuprum nickle duplex metal nano granule |
| CN101161377A (en) * | 2006-10-11 | 2008-04-16 | 三星电机株式会社 | Methods for surface modification of non-dispersible metal nanoparticles and modified metal nanoparticles for inkjet by the same method |
| KR20080057407A (en) * | 2006-12-20 | 2008-06-25 | 주식회사 포스코 | Method of surface treatment of metal particle using self assembly, metal particle thereby, making method of polymer solution containing the metal particle and coating steel panel thereby |
| CN101049918A (en) * | 2007-05-11 | 2007-10-10 | 北京化工大学 | Method for preparing CdTe Nano grains possible to be dissolved in water and organic solvent |
| CN101259531A (en) * | 2008-03-31 | 2008-09-10 | 河南大学 | Surface finish nano copper/copper alloy particles and preparation thereof |
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