CN102554217B - Water-soluble nano-copper and preparation method thereof - Google Patents
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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, as an important branch of metal nano material, because its special physicochemical properties are widely used in the fields such as electrically-conducting paint, electrode material, magnetic fluid, catalysis, especially shows its wide application prospect as Novel lubricating material.But the specific area of pure nano copper particle is large, chemism is high, very easily oxidized in atmosphere and lose original physicochemical characteristics, and bad dispersibility in media as well, easily produce precipitation.The defect of nano copper particle stability and bad dispersibility significantly limit its application in industrial circle, therefore needs to carry out finishing to Nanometer Copper.
In recent years about the preparation of surface finish nano copper particulate, the research of properties and application are at home and abroad paid close attention to widely always.In-situ surface finishing technology is while nanoparticle is formed, and dressing agent carries out coated to nanoparticle, effectively can control the reunion of nano particle and raising and improve its dispersiveness in media as well and stability.Wherein Nanometer Copper Clusters (Monolayer-Protected Cluster the Molecules of the monolayer protection of in-situ surface finishing; be called for short Cu MPC) be different from the Metal copper nanoparticles utilizing additive method to prepare; they normally utilize has the organic molecule of extremely strong affinity as part with metallic copper, and nano copper particle and organic ligand are assembled by the form of covalency or coordination and formed supramolecular system.The advantages such as these MPC have higher stability usually, can repeatedly be separated from solvent and disperse, easy preparation.
At present, the preparation of the Nanometer Copper Clusters that organic monolayer is modified mainly concentrates on oil-soluble Nanometer Copper (organosol of copper) aspect, and the research of Water-soluble nano-copper (hydrosol of copper) is less.Such as, He'nan University opens the human hairs such as the bright eighteenth of the twenty and understands employing in-situ surface finishing technology, has prepared oil solubility nanometer copper (organosol) (publication number CN 101259531A) by solution phase chemical reduction.And test Nanometer Copper, as lube oil additive, there is good extreme-pressure anti-wear effect and excellent antioxygenic property, achieve suitability for industrialized production, but its application can only be confined in apolar medium.The people such as O.Tzhayik have prepared the Nanometer Copper hydrosol using xanthic derivative as dressing agent, but its stabilization time is shorter, easily produces precipitation; See O.Tzhayik.etal., Langmuir., (2002) 18:3364.Existing Nanometer Copper organosol and the hydrosol because of can not water-soluble or poor stability in water, using aqueous phase in the commercial Application of medium as in aqueous cutting fluid and aqueous catalysis, be difficult to the lubrication and the catalytic performance that play its due excellence.Consider from environmental friendliness and economic angle, the research and development of water-base nano copper are a kind of development trends simultaneously, therefore develop effectively to disperse in aqueous phase and the Metal copper nanoparticles of stable existence has important theory significance and practical value.
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 at typical condition stable existence, the metal nano copper particulate of stable dispersion can be formed with the form of " dissolving " in water.
The technical solution used in the present invention is as follows:
A kind of Water-soluble nano-copper, described Nanometer Copper is the Nanometer Copper Clusters of the stable organic supramolecular finishing that the surface being bonded to metallic copper nanoparticle containing sulfydryl organic compound coating material is formed, and structural formula is as follows:
，
Wherein R is straight or branched alkyl, and 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 still further provides a kind of preparation method of Water-soluble nano-copper, the first mixed-alkali solution of preparation containing reducing agent, coating material, then copper precursor solution is joined in above-mentioned mixed solution, be react 0.5-10 h under the alkali condition of 9-14 at pH, obtain described 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 the mixture of one or more in copper sulphate, copper chloride, copper nitrate, Schweinfurt green, Kocide SD.
The concentration of copper precursor solution is 0.1-1 mol/L.
Described reducing agent is the mixture of one or more in formaldehyde, sodium borohydride, sodium hypophosphite, hydrazine hydrate, ascorbic acid.
Reductant solution concentration is 0.02-2mol/L, and the concentration of dressing agent solution is 0.02-1mol/L.
The solvent of reaction system is water or ethanol water.
Adopt the pH value of one or more adjustment reaction systems following: NaOH, urea, ammoniacal liquor, ethylenediamine, diethylamine or triethanolamine.
React on 10-80 DEG C to carry out.
Nanometer Copper of the present invention refers to that coating material contains the Nanometer Copper Clusters (Monolayer-Protected Clusters is called for short MPC) that sulfydryl organic compound is bonded to the stable organic supramolecular finishing of the surface formation of metallic copper nanoparticle.
The invention provides a kind of particle diameter and the homogeneous controlled nano copper particle of pattern, particle size is between 1-25 nm and be evenly distributed, antioxygenic property and the favorable dispersibility in water, can repeatedly be separated in water and disperse, can not produce irreversible reunion Sum decomposition, and this colloidal sol can obtain the Nanometer Copper product of powder after spraying dry.In the preparation, the angle of the present invention from in-situ surface finishing nanoparticle and the angle of MOLECULE DESIGN viewpoint, more deep research has been done to the surface modification of metallic copper nanoparticle, found that, finishing has sulfhydryl compound and the nano-particle of copper that periphery is connected with the hydrophilic functional groups of polarity not only has homogeneous particle diameter and pattern, and in aqueous phase, have good dispersiveness and stability.Concrete, in Liquid reduction reaction process process namely when nano-particle of copper tentatively generates, coating material is incorporated into the surface of nano-particle of copper by the mode of coordinate bond or other strong chemical bonds, so just change the surface microstructure of nano-particle of copper, ensure that nano-particle of copper with the dispersion of the form of single particulate in media as well.Such one side prevents the generation of growing up further and reuniting of copper nano-particle, and the coating function of coating material also prevents the aerial oxidation of metallic copper nanoparticle simultaneously, improves its stability.In addition on the one hand, by changing the polarity of dressing agent and contained functional group thereof, the designability of nano-particle of copper surface texture can be realized, reaching the object of dispersion in particular medium (water).
The novel metal Nanometer Copper hydrosol (powder) obtained can be used for the industrial circles such as water based additive for metal machining liquid, water base lubricant, microcircuit card processing, Ceramic manufacturing, catalyst.
The present invention, relative to prior art, has following advantage:
The present invention can obtain and effectively can disperse and the Metal copper nanoparticles of stable existence in aqueous phase, and simply, cheaper starting materials is easy to get, and production cost is low, and productive rate is high for preparation technology and equipment, is applicable to large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is the uv-visible absorption spectroscopy figure of the Nanometer Copper hydrosol (i.e. Water-soluble nano-copper) of differential responses time acquisition under embodiment 1 condition; In the reaction time of abscissa representative in figure, as can be seen from the figure, along with the increase in reaction time, the Nanometer Copper hydrosol strengthens gradually at the absworption peak at 410 nm places, and describe the increase of Metal copper nanoparticles along with the reaction time, grain size increases gradually.
Fig. 2 is the photo of the Nanometer Copper hydrosol of differential responses time acquisition in Fig. 1; As can be seen from the figure, along with the carrying out of reaction, the color of the Nanometer Copper hydrosol changes yellow into by colourless gradually, the formation of this interval scale Nanometer Copper nucleus, subsequently along with the increase in reaction time, its color changes redness, peony into by yellow gradually, and this shows the increase along with the reaction time, Metal copper nanoparticles is through " Oswald that moral " maturing process, and nanoparticle is grown up gradually.
Fig. 3 is the HRTEM figure of the Nanometer Copper hydrosol that embodiment 3 obtains; As can be seen from the figure, the size of Metal copper nanoparticles 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 Nanometer Copper powder after the Nanometer Copper hydrosol spraying dry of embodiment 1 acquisition.As can be seen from the figure, through XPS analysis, the total copper Cu of powder sample
2p3/2combination can at 932.7ev, this Nanometer Copper obtained is with metallic state, instead of 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.Therefrom can see, in pure TGA molecule, (curve is 2550 cm a)
-1for V
s-Hcharacteristic absorption peak, but this characteristic peak disappears in the infrared spectrum of the Nanometer Copper (curve b) of modified, describes that TGA molecule and copper are surperficial to be connected by 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, describe nanoparticle to COO
-molecular vibration there is obvious impact, also illustrate that simultaneously through modification after nano-particle surface may there is hydrogen bond action.
Fig. 6 is the infrared spectrogram of the nano-particle of copper of embodiment 4 cysteine and modification thereof.As seen from the figure, in pure cysteine molecule, (curve is 2550 cm a)
-1for V
s-Hcharacteristic absorption peak, but this characteristic peak disappears in the infrared spectrum of the Nanometer Copper (curve b) of modified, describes that cysteine molecule and copper are surperficial to be connected by S-H key.Be positioned at 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, describe the COO of nanoparticle to cysteine
-there is not obvious impact in molecular vibration.Combine Fig. 5,6 known: the S-H key in dressing agent molecule is destroyed, and N-H, C=O, C-O key does not destroy, illustrate that TGA and cysteine, by sulfydryl and Metal copper nanoparticles surface, bonding occurs, this with describe in Nanometer Copper structural formula above consistent, TGA and cysteine by the surface successfully modified in Nanometer Copper, and this just Metal copper nanoparticles there is good water miscible reason.
Fig. 7 is that the optical photograph after 0.5 hour, 1 day, 15 days placed respectively by the Nanometer Copper hydrosol obtained under embodiment 4 condition.As can be seen from the figure, along with the prolongation of standing time, the color of the Nanometer Copper hydrosol there occurs change, gradually from light to dark, but does not find significantly to reunite and deposited phenomenon, illustrates that Nanometer Copper prepared by the method has long-term good dispersion stabilization.
Detailed description of the invention
With specific embodiment, technical scheme of the present invention is described below, but protection scope of the present invention is not limited thereto:
Embodiment 1
To in 80 mL distilled water, add 15 mL NH successively
3h
2o, 0.016 mol TGA, 5 mL 80%(mass concentrations, lower same) hydrazine hydrate, then transfer them in 500 mL three-neck flasks, be stirred to and dissolve completely, now solution is water white transparency, is denoted as system I; By 0.032 mol CuSO
45H
2o puts into beaker, adds 100 mL distilled water and dissolves completely, and solution is blue, is denoted as system II; And being slowly added drop-wise in above-mentioned I mixed solution by II, constant temperature 80 DEG C is reaction 1 h fully, finally obtains the Nanometer Copper hydrosol of reddish brown, and this Nanometer Copper hydrosol can dispersion steady in a long-term and without coagulation in water.
Embodiment 2
To in 85 mL distilled water, add 15 mL NH successively
3h
2o, 0.016mol TGA, 0.6048 g(0.016mol) NaBH
4, then transfer them in 500 mL three-neck flasks, be stirred to and dissolve completely, now solution is water white transparency, is denoted as system I; By 0.032 mol Cu (NO
3)
23H
2o puts into beaker, adds 100 mL distilled water and dissolves completely, and solution is blue, is denoted as system II; And being slowly added drop-wise in above-mentioned I mixed solution by II, constant temperature 60 DEG C fully reacts 2h, finally obtains the Nanometer Copper hydrosol of reddish brown, and this Nanometer Copper hydrosol can dispersion steady in a long-term and without coagulation in water.
Embodiment 3
To in 80 mL distilled water, add 15 mL NH successively
3h
2o, 0.016 mol TGA, 5 mL 80% hydrazine hydrates, then transfer them in 500 mL three-neck flasks, be stirred to and dissolve completely, now solution is water white transparency, is denoted as system I; By 0.032 mol Cu (OH)
2put into beaker, add 100 mL distilled water and disperse completely, system is blue, is denoted as system II; And being slowly added drop-wise in above-mentioned I mixed solution by II, constant temperature 40 DEG C is reaction 2 h fully, finally obtain the Nanometer Copper hydrosol of reddish brown, and this Nanometer Copper hydrosol can dispersion steady in a long-term and without coagulation in water.
Embodiment 4
To in 19 mL distilled water, add 0.52 g NaOH, 1 mL 80% hydrazine hydrate, 0.7754 g cysteine successively, then transfer them in 100 mL three-neck flasks, be stirred to and dissolve completely, now solution is water white transparency, is denoted as system I; By 0.032 mol Cu (OH)
2put into beaker, add 100 mL water and disperse completely, system is blue, is denoted as system II; And being slowly added drop-wise in above-mentioned I mixed solution by II, constant temperature 40 DEG C is reaction 2 h fully, finally obtain the Nanometer Copper hydrosol of rufous, and this Nanometer Copper hydrosol can dispersion steady in a long-term and without coagulation in water.
Embodiment 5
To in 80 mL distilled water, add 15 mL NH successively
3h
2o, 0.005 mol mercaptopropanesulfonic acid sodium, 5 mL80% hydrazine hydrates, then transfer them in 500 mL three-neck flasks, be stirred to and dissolve completely, now solution is water white transparency, is denoted as system I; By 0.032 mol CuSO
45H
2o puts into beaker, adds 100 mL distilled water and dissolves completely, and solution is blue, is denoted as system II; And being slowly added drop-wise in above-mentioned I mixed solution by II, constant temperature 40 DEG C is reaction 6 h fully, finally obtain the Nanometer Copper hydrosol of reddish brown, and this Nanometer Copper hydrosol can dispersion steady in a long-term and without coagulation in water.
Embodiment 6
To in 80 mL distilled water, add 15 mL NH successively
3h
2o, 0.005 mol mercaptoethylamine hydrochloride, 5 mL80% hydrazine hydrates, then transfer them in 500 mL three-neck flasks, be stirred to and dissolve completely, now solution is water white transparency, is denoted as system I; By 0.032 mol CuSO
45H
2o puts into beaker, adds 100 mL distilled water and dissolves completely, and solution is blue, is denoted as system II; And being slowly added drop-wise in above-mentioned I mixed solution by II, constant temperature 20 DEG C is reaction 6 h fully, finally obtain the Nanometer Copper hydrosol of reddish brown, and this Nanometer Copper hydrosol can dispersion steady in a long-term and without coagulation in water.
Embodiment 7
To in 80 mL distilled water, add 15 mL triethanolamines, 0.016 mol TGA, 5 mL 80% hydrazine hydrates successively, then transfer them in 500 mL three-neck flasks, be stirred to and dissolve completely, now solution is water white transparency, is denoted as system I; By 0.032 mol Cu (OH)
2put into beaker, add 100 mL distilled water and disperse completely, system is blue, is denoted as system II; And being slowly added drop-wise in above-mentioned I mixed solution by II, constant temperature 40 DEG C is reaction 2 h fully, finally obtain the Nanometer Copper hydrosol of reddish brown, and this Nanometer Copper hydrosol can dispersion steady in a long-term and without coagulation in water.
Embodiment 8
To in the mixed solution containing 20 ml ethanol and 80 mL distilled water, add 15 mL NH successively
3h
2o, 0.016 mol TGA, 5 mL 80%(mass concentrations, lower same) hydrazine hydrate, then transfer them in 500 mL three-neck flasks, be stirred to and dissolve completely, now solution is water white transparency, is denoted as system I; By 0.032 mol CuCl
2put into beaker, add 100 mL distilled water and dissolve completely, solution is blue, is denoted as system II; And being slowly added drop-wise in above-mentioned I mixed solution by II, constant temperature 80 DEG C is reaction 1 h fully, finally obtains the Nanometer Copper hydrosol of reddish brown, and this Nanometer Copper hydrosol can dispersion steady in a long-term and without coagulation in water.
Above-described embodiment is the preferred embodiment of the present invention, but embodiments of the present invention are not restricted to the described embodiments, and the change that other any the present invention of not deviating from does all should be equivalent substitute mode, is included within protection scope of the present invention.
Claims (7)
1. the preparation method of a Water-soluble nano-copper, it is characterized in that, first the mixed-alkali solution of preparation containing reducing agent, coating material, then joins in above-mentioned mixed solution by copper precursor solution, be react 0.5-10 h under the alkali condition of 9-14 at pH, obtain described Water-soluble nano-copper; The presoma of described copper is Kocide SD, and the pH value of reaction system adopts one or more adjustment in urea, ethylenediamine, diethylamine or triethanolamine; The amount of substance ratio that feeds intake of copper presoma, reducing agent, coating material is 1:0.1-10:0.1-10; Described Water-soluble nano-copper is the Nanometer Copper Clusters of the stable organic supramolecular finishing that the surface being bonded to metallic copper nanoparticle containing sulfydryl organic compound coating material is formed, and structural formula is as follows:
，
Wherein R is straight or branched alkyl, and 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 Water-soluble nano-copper as claimed in claim 1, it is characterized in that, described reducing agent is the mixture of one or more in formaldehyde, sodium borohydride, sodium hypophosphite, hydrazine hydrate, ascorbic acid.
3. the preparation method of Water-soluble nano-copper as claimed in claim 1, it is characterized in that, the solvent of reaction system is water or ethanol water.
4. the preparation method of Water-soluble nano-copper as claimed in claim 1, it is characterized in that, the concentration of copper precursor solution is 0.1-1 mol/L.
5. the preparation method of Water-soluble nano-copper as claimed in claim 1, it 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.
6. the preparation method of the Water-soluble nano-copper as described in one of claim 1-5, is characterized in that, reacts on 10-80 DEG C and carries out.
7. the Water-soluble nano-copper that the preparation method of the Water-soluble nano-copper according to claim 1-6 obtains.
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| CN103084581B (en) * | 2013-01-08 | 2015-02-04 | 河南大学 | Preparation method for copper nanowire |
| CN103264167A (en) * | 2013-06-09 | 2013-08-28 | 南通众诚生物技术有限公司 | Surface modification nanometer copper particle and preparation method thereof |
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