CN105177696B - A kind of preparation method of the copper nano structural material of morphology controllable - Google Patents
A kind of preparation method of the copper nano structural material of morphology controllable Download PDFInfo
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- CN105177696B CN105177696B CN201510531006.6A CN201510531006A CN105177696B CN 105177696 B CN105177696 B CN 105177696B CN 201510531006 A CN201510531006 A CN 201510531006A CN 105177696 B CN105177696 B CN 105177696B
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Abstract
The present invention relates to a kind of hot method controllable method for preparing of the alcohol of copper nanostructured.The present invention is to provide energy by the metallic copper in the high temperature and high pressure environment by pressure vessel (such as autoclave) to zero-valent state, controls temperature and the retention time of alcoholic solution, the copper nanostructured of pattern required for very easily obtaining.Method is to insert ethanol solution and the simple metal copper sheet cleaned up in autoclave, and copper sheet is fully immersed in the ethanol solution.Autoclave is maintained at into 100 200 DEG C to react 0.5 6 hours or more, certain temperature keeps different time to can obtain nanometer sheet, nano wire and nanoparticle structure.The copper nanostructured obtained by simple alcohol hot preparation method has inexpensive application prospect in microelectronic integrated circuit, catalysis, antibacterial field.
Description
Technical field
The present invention relates to the preparing technical field of nano material, the copper nano structural material of more particularly to a kind of morphology controllable
Preparation method.
Background technology
Copper nanostructured is with its excellent optics, electrically and thermally performance and relatively low price, in catalysis, antibacterial
There is important application in field, in microelectronic integrated circuit field, it has also become the most frequently used wire in conventional circuit, and in large quantities
As the interconnector in microelectronic integrated circuit.Research about the nanostructured of copper starts from 1950s.Copper whisker
(including nano wire, nanometer rods and nanotube etc.) can be obtained by hydrogen reducing halide (such as CuCl, CuI, CuBr)
(S.S.Brenner,Acta Metallurgica,1956,4,62).Since 1990s, along with nanosecond science and technology
Development, researcher has carried out substantial amounts of research to copper nanostructured.The preparation method of current copper nanostructured has liquid phase synthesis
Method；Gas phase synthesis method and template synthesis method.Liquid phase synthesizing method usually using hydrazine hydrate (A.R.Rathmell, S.M.Bergin,
Y.L.Hua, Z.Y.Li, B.J.Wiley, Adv.Mater, 2010,22,3558), glucose (M.Jin, G.He, H.Zhang,
J.Zeng, Z.Xie, Y.Xia, Angew.Chem.Int.Ed., 2011,50,10560) and two ligand systems (D.Zhang,
R.Wang, M.Wen, D.Weng, X.Cui, J.Sun, H.Li, Y.Lu, J.Am.Chem.Soc., 2012,134,14283) conduct
Reducing agent prepares copper nanostructured on a large scale, although the method that the above prepares copper nanostructured can prepare better performances
Copper nanostructured, but in most cases, in order to control copper nanostructured morphologies, and prevent to reunite, also need to add steady
Determine agent or function inorganic matter.But these reducing agents and additive are often covered in copper nanostructured surface and cause it to inactivate
(Y.Tan,X.Xue,Q.Peng,H.Zhao,T.Wang,Y.Li,Nano Lett.,2007,7,3723；S.Deki,
K.Akamatsu,T.Yano,M.Mizuhata,A.J.Kajinami,Mater.Chem.,1998,8,1865).Vapor phase method is system
A kind of typical method (the S.N.Mohammad.Nano Lett., 2008,8,1532 of standby copper nanostructured；H.Choi,
J.Am.Chem.Soc., 2004,126,6248), but it is related to cumbersome processing procedure, such as, high-temperature heating copper predecessor makes it
Evaporation, then allows steam to flow through the at a fairly low solid phase substrate of a temperature for being loaded with catalyst, the substrate also needs a supporting temperature
The controllable Cryo Equipment of degree, so that steam can be condensed and deposit (W.A.Bryant.J.Mater.Sci., 1977,12:
1285).Template is probably to prepare the method that copper nanostructured is most generally used, but this method also includes many steps, and production
Amount it is very low (A.Mignani, B.Ballarin, E.Boanini, M.C.Cassani, Electrochim.Acta, 2014,115,
537；S.Shin,B.S.Kim,K.M.Kim,B.H.Kong,H.K.Cho,H.H.Cho,J.Mater.Chem.,2011,21,
17967)。
The content of the invention
It is an object of the invention to provide a kind of preparation method of the copper nano structural material of morphology controllable, current system is solved
Standby copper nanostructured need to widen the source of predecessor using cupric as the limitation of predecessor；And process is simple, operation side
Just, controllability is strong, without the organic principles such as any surfactant, stabilizer and complex instrument and equipment.
The present invention solve the scheme that is used of above-mentioned technical problem for：A kind of system of the copper nano structural material of morphology controllable
Preparation Method, it is characterized in that a certain amount of alcoholic solution and the simple metal copper foil or copper sheet that clean up are inserted in autoclave, and entirely
Portion is immersed in the alcoholic solution, autoclave is kept at a certain temperature a period of time can obtain required copper nano junction
Structure.
By such scheme, described alcoholic solution is absolute ethyl alcohol, described copper foil or copper sheet be purity 99wt.% with
On.
By such scheme, the temperature of described autoclave is maintained between 100-200 DEG C.
By such scheme, the temperature of described autoclave is preferably 160 DEG C.
By such scheme, the described retention time is 0.5-8 hours.
The preferred time that the present invention prepares copper nanometer sheet, copper nano-wire and copper nano particles is respectively 1.5 hours, 3 hours
With 6 hours.
The present invention principle be：All processes that nature occurs all must comply with the first law of thermodynamics, keep energy
Conservation.In the autoclave of HTHP, alcohol thermal response system has much higher energy than extraneous natural environmental condition, because
This, the copper foil (piece) in autoclave obtains very high energy, and these high-energy cause the crystal grain for constituting metal copper sheet to enter
Rearrangement, is grown towards the higher composition structure of maximum system energy, therefore, the initial shape in common metal copper foil (piece) surface
The irregular copper micro-structural of shape can become with the high copper micro-structural of comparison rule profile energy comparison after energy is obtained.It is many
Well known, in crystal growing process, the reduction of surface energy is the motive power that simple particle increases, the minimum process of surface energy
The Morphology Evolution of system will be caused, however, metal copper foil (piece) at high temperature under high pressure is not in accordance with itself Gibbs free energy
What the spontaneous direction reduced was carried out, but what the direction increased towards maximum system energy was carried out.So when metal copper foil (piece) is in height
Residing temperature is different with the retention time in pressure kettle, and the energy of acquisition is also different, and system transition is also different into copper nanostructured.Cause
This, provides energy, alcohol is molten in control by the metallic copper in the high temperature and high pressure environment of pressure vessel (such as autoclave) to zero-valent state
The temperature and time of liquid, the copper nanostructured of pattern required for can very easily being obtained using the hot method of alcohol.The present invention is certain
Temperature keep different time to can obtain the copper micro-structural of nanometer sheet, nano wire and nanoparticle structure.
Beneficial effects of the present invention：First utilize zero-valent state metallic copper, the HTHP having by the hot method of alcohol and
The environment of anaerobic, without any template, complex instrument, surfactant and without chemically reacting, by common copper foil (or copper
Piece) be placed in anhydrous alcohol solution, by control temperature and time, directly obtain pattern in the irregular copper surface of pattern can
The copper nanostructured of control；The present invention has generality, simple, easy, large-scale production can be achieved, it is in the integrated electricity of microelectronics
Road, catalysis, antibacterial field have inexpensive application prospect.
Brief description of the drawings
Fig. 1 is the XRD of the metal copper foil (piece) before and after the hot method reaction of alcohol；
Fig. 2 is the SEM pictures of blank simple metal copper sheet and the copper nanostructured prepared；
Fig. 3 is the open-circuit photovoltage curve map under pulsed visible-light irradiation of the metal copper foil (piece) before and after reaction.
Embodiment
The inventive method and effect are further illustrated below by embodiment.
Embodiment 1：
Prepared by copper nanometer sheet, preparation process is：
1st, the cleaning of substrate：By simple metal copper sheet (2.5 × 6cm2) be immersed in watery hydrochloric acid more than 10 minutes, take out, use
A large amount of water are rinsed, then are carefully scrubbed with banister brush, and then, with deionized water, acetone, alcohol is respectively cleaned by ultrasonic 10 minutes, are taken out,
It is standby after drying；
2nd, ethanol solution 80ml is taken, is poured into autoclave.The simple metal copper sheet cleaned up is inserted into autoclave again
In, allow copper sheet to be fully immersed in ethanol solution during placement；
3rd, autoclave is put into air dry oven, sets the temperature inside the box as 160 DEG C, the retention time is 3 hours；
4th, 3 hours relief autoclave natural coolings, take out copper sheet, at this moment find that simple metal copper sheet becomes after the hot method of alcohol
The golden yellow that color is more uniformly distributed, golden yellow film that this layer of color is more uniformly distributed is exactly the copper nano-wire prepared.
Fig. 1 shows the XRD of Fig. 1 (a) and Fig. 1 (b) copper nano-wire after reaction before the hot method reaction of the metal copper sheet alcohol.
Fig. 1 (a) as diffraction maximum, corresponds to (111) of metallic copper, (200) respectively at three in the metal copper sheet included in Fig. 1 (b)
(220) crystal face, this illustrates that metal copper sheet does not have the life of new thing phase in pure ethanol solution after alcohol thermal response
Into.But by Fig. 1 (b) and (a) paired observation, it is seen that the position of the maximum diffraction maximum of relative intensity is differed in the two collection of illustrative plates
Sample, most strong diffraction maximum correspondence (220) crystal face of the metal copper sheet without alcohol thermal response, and occur maximum intensity after alcohol thermal response
Diffraction maximum is (200) crystal face, is illustrated after the alcohol thermal response of HTHP, and the metal copper sheet becomes<200>Selected on direction
Tachyauxesis.It is because while in alcohol thermal process do not have novel substance generation, but metal copper sheet is knitted in alcohol thermal process
Structure effect (textured effect) so that the lattice of metal copper sheet is changed.
Fig. 2 (a) and 2 (f) show before the hot method effect of metal copper sheet alcohol and effect 3 hours after irregular copper micro-structural and
Copper nano-wire micro-structural.
Fig. 3 is nano wire copper sheet Fig. 3 (a) and open circuit light of the metal copper plate electrode Fig. 3 (b) under intermittent radiation of visible light
Voltage changes over time curve map.As can be seen that nano wire copper sheet is generated under intermittent radiation of visible light from Fig. 3 (a)
Corresponding regularly changing open-circuit photovoltage.And from Fig. 3 (b) as can be seen that metal copper plate electrode shines in intermittent visible ray
Penetrate lower without the corresponding regularly changing open-circuit photovoltage of generation.So, the generation of open-circuit photovoltage is necessarily due to nanometer
Caused by nano wire pattern micro-structural on line copper sheet.In the case of open circuit, it is seen that light irradiation causes on copper nano-wire
Electronics is photic to be transmitted into solvent, the accumulation of positive charge then occurs on metal electrode, causes the potential of electrode to raise.
Embodiment 2：
Except the reaction time in step 3 in embodiment 1 is changed into 0.5,1,1.5,2 and 4 hour outer, holding embodiment 1
In all operating condition and step it is constant, obtain pattern for Fig. 2 (b), Fig. 2 (c), Fig. 2 (d), Fig. 2 (e) and Fig. 2 (g) shown
Copper multiaspect bulk microstructure, nanometer sheet micro-structural and copper nano-wire and nano particle micro-structural coexists, its photoelectric properties and reality
Apply example 1 similar.
Embodiment 3：
In addition to the reaction time in step 3 in embodiment 1 is changed into 6 hours, operation bar all in embodiment 1 is kept
Part and step are constant, and its pattern is the copper nano particles micro-structural shown in Fig. 2 (h), and its photoelectric properties and embodiment 1 are similar.
Embodiment 4：
In addition to the reaction time in step 3 in embodiment 1 is changed into 8 hours, operation bar all in embodiment 1 is kept
Part and step are constant, and its pattern is similar with the copper nano particles micro-structural shown in Fig. 2 (h), its photoelectric properties and the phase of embodiment 1
Seemingly.
Claims (2)
1. the preparation method of the copper nano structural material of a kind of morphology controllable, it is characterized in that a certain amount of alcoholic solution and cleaning is dry
Net simple metal copper foil or copper sheet are inserted in autoclave, and described alcoholic solution is absolute ethyl alcohol, and described copper foil or copper sheet are pure
Degree is fully immersed in the alcoholic solution in more than 99wt.%, and autoclave is kept into a period of time at a certain temperature
Required copper nanostructured is obtained, the temperature of described autoclave is maintained between 100-200 DEG C, the described retention time is
0.5-8 hours.
2. the preparation method of the copper nano structural material of the morphology controllable as described in claim 1, it is characterized in that described high pressure
The temperature of kettle is 160 DEG C.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1381328A (en) * | 2001-04-18 | 2002-11-27 | 中国科学院化工冶金研究所 | Process for preparing superfine (nano) metal powder by hydrogen reduction of polyol |
| CN101407332A (en) * | 2007-10-12 | 2009-04-15 | 新疆大学 | Hydro-thermal synthesis method for cupric oxide nano-rod |
| CN102586800A (en) * | 2011-01-17 | 2012-07-18 | 李小毛 | Preparation method of nano-copper powder |
| CN102730651A (en) * | 2012-07-08 | 2012-10-17 | 桂林理工大学 | Solvothermal method for regulating morphology of elemental nano-selenium |
| CN104057099A (en) * | 2014-06-09 | 2014-09-24 | 上海交通大学 | Ultrathin nano-porous copper foil preparation method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20140213427A1 (en) * | 2013-01-31 | 2014-07-31 | Sunpower Technologies Llc | Photocatalyst for the Reduction of Carbon Dioxide |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1381328A (en) * | 2001-04-18 | 2002-11-27 | 中国科学院化工冶金研究所 | Process for preparing superfine (nano) metal powder by hydrogen reduction of polyol |
| CN101407332A (en) * | 2007-10-12 | 2009-04-15 | 新疆大学 | Hydro-thermal synthesis method for cupric oxide nano-rod |
| CN102586800A (en) * | 2011-01-17 | 2012-07-18 | 李小毛 | Preparation method of nano-copper powder |
| CN102730651A (en) * | 2012-07-08 | 2012-10-17 | 桂林理工大学 | Solvothermal method for regulating morphology of elemental nano-selenium |
| CN104057099A (en) * | 2014-06-09 | 2014-09-24 | 上海交通大学 | Ultrathin nano-porous copper foil preparation method |
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