CN105483795A - Method for preparing composite copper nanowire with underpotential deposition technology - Google Patents
Method for preparing composite copper nanowire with underpotential deposition technology Download PDFInfo
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- CN105483795A CN105483795A CN201610041385.5A CN201610041385A CN105483795A CN 105483795 A CN105483795 A CN 105483795A CN 201610041385 A CN201610041385 A CN 201610041385A CN 105483795 A CN105483795 A CN 105483795A
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- copper nano
- wire
- underpotential deposition
- deposition
- underpotential
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/045—Anodisation of aluminium or alloys based thereon for forming AAO templates
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
Abstract
The invention relates to the technical field of nano materials, in particular to a method for preparing a composite copper nanowire with an underpotential deposition technology. The method comprises steps as follows: preparing an AAO (anodic aluminum oxide) template; preparing the copper nanowire through electrochemical deposition; forming a metal monatomic layer on the surface of the copper nanowire through underpotential deposition. According to the method, the metal monatomic layer is formed on the copper surface through the underpotential deposition, the composite metal nanowire is prepared, the copper nanowire is prevented from oxidization, meanwhile, the application cost of a transparent conductive material is reduced, the experimental process is simple and convenient, the ultrathin composite metal nanowire can be prepared, furthermore, the dispersibility is good, and the grain sizes are uniform.
Description
Technical field
The present invention relates to technical field of nano material, be specifically related to a kind of method adopting underpotential deposition technology to prepare complex copper nano wire.
Background technology
In order to effectively prevent burning, improve electroconductibility and erosion resistance, traditional method adopts plating.Plating is exactly utilize electrolysis principle to plate the process of other sheet metal or alloy in some metallic surface.But want the composition metal nano wire obtaining ultrathin nanometer structure, electroplate no longer applicable.For the preparation of copper nano-wire, adopt chemical reduction method traditionally more, but experimentation is harsh, also comparatively loaded down with trivial details also undesirable, and copper nano-wire prepared by pure chemistry method is extremely easily oxidized, require higher to experimental installation, the thickness of wayward clad metal, be also unfavorable for its application in transparent conductive material.
The underpotential deposition of metal refers to that a kind of element deposits on another kind of element, and required electromotive force just deposits required electromotive force in this element on self element.Research shows, only has when the metal that work function is less deposits to the metal that work function is larger, just likely underpotential deposition occurs.Copper metal underpotential deposition is the effective ways obtaining dissimilar metal monoatomic layer at copper surface deposition.At present, existing pertinent literature reports the underpotential deposition on the precious metal surfaces such as gold, platinum such as silver, copper, tin, lead, and very few in the research of copper surface underpotential deposition for silver, zinc or nickel.
Summary of the invention
In view of this, be necessary for above-mentioned copper nano-wire easily oxidized, be difficult to the problem at copper nano-wire surface deposition metal monoatomic layer, provide a kind of underpotential deposition technology to prepare the method for complex copper nano wire.
For achieving the above object, the present invention takes following technical scheme:
A kind of method adopting underpotential deposition technology to prepare complex copper nano wire of the present invention, comprising:
The preparation of step 1 porous anodic aluminium oxide (AAO) template: the high-purity aluminium flake surface impurity of first cleaning removing, alkali lye is adopted to remove the zone of oxidation on aluminium flake surface again, then after adopting plating mode to obtain rough AAO template, rough AAO template is put into the phosphoric acid solution that massfraction is 1.5-10%, namely reaming at least 3 minutes, finally totally obtain AAO template with deionized water rinsing;
Step 2 adopts electrochemical deposition to prepare copper nano-wire: configuration concentration is the copper-bath of 0.05mol/L ~ 0.1mol/L, then adds 1-5 gram of boric acid, obtains mixed electrolytic solution; Take AAO as working electrode, carbon-point, for carry out electroplating deposition copper nano-wire to electrode, after deposition terminates, cleans AAO template with deionized water;
Step 3 is at copper nano-wire surface underpotential deposition metal monoatomic layer: be working electrode by the AAO template depositing copper nano-wire, and platinum filament is to electrode, and saturated calomel electrode is reference electrode, and metallic compound is dissolved in H
2sO
4in solution be electrolyte solution, after carrying out underpotential deposition, take out and deposit the AAO template of copper nano-wire, put into alkali lye, removing template, centrifuge washing at least 2 times, obtains the copper nano-wire that surface deposition has metal monoatomic layer.
Further, the high-purity aluminium flake surface impurity described in step 1 adopts ethanolic soln to remove for ultrasonic 20 minutes, then uses washed with de-ionized water.
Further, step 1 and the alkali lye described in step 3 are the sodium hydroxide solution of 1mol/L.
Further, the electroplating technology of the rough AAO template of the acquisition described in step 1 is: make anode with aluminium flake, negative electrode made by carbon-point, and concentration is the oxalic acid solution of 0.1mol/L ~ 1.0mol/L is electrolytic solution, and under the condition of 20 ~ 60V constant voltage, Keep agitation obtains.
Further, described in step 2, electroplating deposition copper nano-wire is: the constant 10V of voltage of alternating current, and depositing time is prepare copper nano-wire in 10 ~ 100 minutes.
Further, described in step 3, metallic compound is dissolved in H
2sO
4in solution, the metallic compound for 0.1mmol/L ~ 0.01mol/L is dissolved in the H of 0.1mol/L
2sO
4in solution.
Further, described metallic compound described in step 3 is AgNO
3(or Zn (NO
3)
2, Ni (NO
3)
2).
Further, described in step 3, copper nano-wire surface underpotential deposition process is: under room temperature, under 0 ~ 1.0V current potential, carry out cycle potentials scanning, underpotential deposition 20s ~ 60s with the speed of sweeping of 10mV/s.
Further, phosphoric acid solution massfraction described in step 1 is 5%, and pore-enlargement is 10 minutes; Boric acid consumption described in step 2 is 3 grams; Centrifuge washing described in step 3 is three times.
Beneficial effect of the present invention is:
The present invention at copper surface deposition metal monoatomic layer by undercurrent potential, is prepared composition metal nano wire, prevents the oxidation of copper nano-wire, reduces transparent conductive material application cost simultaneously.The inventive method successfully can obtain the composite material of metal monoatomic layer coated copper nano wire, and experimentation of the present invention is easy, can prepare ultra-thin composition metal nano wire, and good dispersity, uniform particle diameter.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly, below in conjunction with the embodiment of the present invention, do to describe clearly and completely further to technical scheme of the present invention.It should be noted that, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Employing underpotential deposition technology of the present invention prepares the method for complex copper nano wire, comprising: the preparation of porous anodic aluminium oxide (AAO) template; Electrochemical deposition is adopted to prepare copper nano-wire; Underpotential deposition metal monoatomic layer is utilized on copper nano-wire surface.
The preparation of described porous anodic alumina template, comprises ultrasonic for high-purity aluminium flake ethanolic soln 20 minutes removing surface impurities, then uses washed with de-ionized water; Cleaned aluminium flake is used successively sodium hydroxide solution and the washed with de-ionized water of 1mol/L, to remove the zone of oxidation on aluminium flake surface; Make anode with the aluminium flake handled well, negative electrode made by carbon-point, and concentration is the oxalic acid solution of 0.1mol/L ~ 1.0mol/L is electrolytic solution, and Keep agitation under the condition of 20 ~ 60V constant voltage, obtains rough AAO template; Rough AAO template is put into the phosphoric acid solution that massfraction is 1.5-10%, reaming at least 3 minutes, finally clean with deionized water rinsing, obtain AAO template.Preferably, described phosphoric acid solution massfraction is 5%, and pore-enlargement is 10 minutes.
Described electrochemical deposition prepares copper nano-wire, comprises the copper-bath that configuration concentration is 0.05mol/L ~ 0.1mol/L, then adds 1-5 gram of boric acid, obtains mixed electrolytic solution; Take AAO as working electrode, carbon-point is to electrode, and voltage of alternating current is constant is 10V, and depositing time is prepare copper nano-wire in 10 ~ 100 minutes; After deposition terminates, clean AAO template with deionized water.Preferably, described boric acid consumption is 3 grams.
Described copper nano-wire surface utilizes underpotential deposition metal monoatomic layer, the AAO template comprising depositing copper nano-wire is working electrode, platinum filament is to electrode, and saturated calomel electrode is reference electrode, and electrolyte solution is the metallic compound of 0.1mmol/L ~ 0.01mol/L and the H of 0.1mol/L
2sO
4solution, under room temperature, under 0 ~ 1.0V current potential, carries out cycle potentials scanning, underpotential deposition 20s ~ 60s with the speed of sweeping of 10mV/s.Finally AAO template taken out, put into the NaOH solution of 1mol/L, removing template, centrifuge washing at least 2 times, obtains the copper nano-wire that surface deposition has metal monoatomic layer.Preferably, described centrifuge washing is three times.
In electrolyte solution of the present invention, metallic compound is AgNO
3(or Zn (NO
3)
2, Ni (NO
3)
2); The metal monoatomic layer that described underpotential deposition obtains is silver, zinc or nickel dam.
Embodiment 1
The silver-colored monoatomic layer underpotential deposition in copper nano-wire surface: the AgNO AAO template depositing copper nano-wire being positioned over 0.01mmol/L ~ 0.1mol/L
3with the H of 0.1mol/L
2sO
4underpotential deposition 20s ~ 60s in solution, completes the deposition of silver-colored monoatomic layer.
Embodiment 2
Copper nano-wire surface zinc monoatomic layer underpotential deposition: the Zn (NO AAO template depositing copper nano-wire being positioned over 0.01mmol/L ~ 0.1mol/L
3)
2with the H of 0.1mol/L
2sO
4underpotential deposition 20s ~ 60s in solution, completes the deposition of zinc monoatomic layer.
Embodiment 3
Copper nano-wire surface nickel monoatomic layer underpotential deposition: the Ni (NO AAO template depositing copper nano-wire being positioned over 0.01mmol/L ~ 0.1mol/L
3)
2with the H of 0.1mol/L
2sO
4underpotential deposition 20s ~ 60s in solution, completes the deposition of nickel monoatomic layer.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (9)
1. adopt underpotential deposition technology to prepare a method for complex copper nano wire, it is characterized in that, comprising:
The preparation of step 1 porous anodic alumina template: the high-purity aluminium flake surface impurity of first cleaning removing, alkali lye is adopted to remove the zone of oxidation on aluminium flake surface again, then after adopting plating mode to obtain rough porous anodic alumina template, rough porous anodic alumina template is put into the phosphoric acid solution that massfraction is 1.5-10%, namely reaming at least 3 minutes, finally totally obtain porous anodic alumina template with deionized water rinsing;
Step 2 adopts electrochemical deposition to prepare copper nano-wire: configuration concentration is the copper-bath of 0.05mol/L ~ 0.1mol/L, then adds 1-5 gram of boric acid, obtains mixed electrolytic solution; Take porous anodic aluminium oxide as working electrode, carbon-point, for carry out electroplating deposition copper nano-wire to electrode, after deposition terminates, cleans porous anodic alumina template with deionized water;
Step 3 is at copper nano-wire surface underpotential deposition metal monoatomic layer: be working electrode by the porous anodic alumina template depositing copper nano-wire, and platinum filament is to electrode, and saturated calomel electrode is reference electrode, and metallic compound is dissolved in H
2sO
4in solution be electrolyte solution, after carrying out underpotential deposition, take out and deposit the porous anodic alumina template of copper nano-wire, put into alkali lye, removing template, centrifuge washing at least twice, obtains the copper nano-wire that surface deposition has metal monoatomic layer.
2. employing underpotential deposition technology according to claim 1 prepares the method for complex copper nano wire, it is characterized in that, the high-purity aluminium flake surface impurity described in step 1 adopts ethanolic soln to remove for ultrasonic 20 minutes, then uses washed with de-ionized water.
3. employing underpotential deposition technology according to claim 1 prepares the method for complex copper nano wire, it is characterized in that, step 1 and the alkali lye described in step 3 are the sodium hydroxide solution of 1mol/L.
4. employing underpotential deposition technology according to claim 1 prepares the method for complex copper nano wire, it is characterized in that, the electroplating technology of the rough porous anodic alumina template of the acquisition described in step 1 is: make anode with aluminium flake, negative electrode made by carbon-point, concentration is the oxalic acid solution of 0.1mol/L ~ 1.0mol/L is electrolytic solution, and under the condition of 20 ~ 60V constant voltage, Keep agitation obtains.
5. employing underpotential deposition technology according to claim 1 prepares the method for complex copper nano wire, and it is characterized in that, described in step 2, electroplating deposition copper nano-wire is: the constant 10V of voltage of alternating current, and depositing time is prepare copper nano-wire in 10 ~ 100 minutes.
6. employing underpotential deposition technology according to claim 1 prepares the method for complex copper nano wire, it is characterized in that, is dissolved in H described in step 3
2sO
4in metallic compound be dissolved in H
2sO
4in solution, the metallic compound for 0.1mmol/L ~ 0.01mol/L is dissolved in the H of 0.1mol/L
2sO
4in solution.
7. the employing underpotential deposition technology according to claim 1 or 6 prepares the method for complex copper nano wire, it is characterized in that, described in be dissolved in H
2sO
4in metallic compound be AgNO
3, Zn (NO
3)
2or Ni (NO
3)
2.
8. employing underpotential deposition technology according to claim 1 prepares the method for complex copper nano wire, it is characterized in that, described in step 3, copper nano-wire surface underpotential deposition process is: under room temperature, under 0 ~ 1.0V current potential, cycle potentials scanning is carried out, underpotential deposition 20s ~ 60s with the speed of sweeping of 10mV/s.
9. employing underpotential deposition technology according to claim 1 prepares the method for complex copper nano wire, it is characterized in that, phosphoric acid solution massfraction described in step 1 is 5%, and pore-enlargement is 10 minutes; Boric acid consumption described in step 2 is 3 grams; Centrifuge washing described in step 3 is three times.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107099817A (en) * | 2017-04-13 | 2017-08-29 | 合肥工业大学 | A kind of preparation method of doped ferric oxide nanometer line ordered array light anode |
| CN110228788A (en) * | 2019-05-22 | 2019-09-13 | 湖北第二师范学院 | A kind of Berzeline nanotube and preparation method thereof, solar battery |
| CN110919023A (en) * | 2019-11-19 | 2020-03-27 | 吉林大学 | Method for preparing multi-dendritic platinum-based nano material by zinc ion induction |
| CN111218702A (en) * | 2019-08-02 | 2020-06-02 | 大连理工大学 | Surface preparation method capable of preparing various nanowire structures |
| CN113279013A (en) * | 2021-05-24 | 2021-08-20 | 北京化工大学 | Monoatomic alloy nanowire catalyst for carbon dioxide electroreduction and preparation method thereof |
| US11282620B2 (en) * | 2018-03-09 | 2022-03-22 | Ohio State Innovation Foundation | Electroplating process for connectorizing superconducting cables |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100261034A1 (en) * | 2006-08-07 | 2010-10-14 | Cardarelli Francois | Composite metallic materials, uses thereof and process for making same |
| CN102677115A (en) * | 2012-05-23 | 2012-09-19 | 天津大学 | Multilayer nanowire and its preparation method by using anodic aluminum oxide template prepared by two-step anodic oxidation |
| CN104616728A (en) * | 2015-01-26 | 2015-05-13 | 河南大学 | Nanometer cable transparent conducting thin film with copper inner core and preparation method thereof |
-
2016
- 2016-01-21 CN CN201610041385.5A patent/CN105483795B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100261034A1 (en) * | 2006-08-07 | 2010-10-14 | Cardarelli Francois | Composite metallic materials, uses thereof and process for making same |
| CN102677115A (en) * | 2012-05-23 | 2012-09-19 | 天津大学 | Multilayer nanowire and its preparation method by using anodic aluminum oxide template prepared by two-step anodic oxidation |
| CN104616728A (en) * | 2015-01-26 | 2015-05-13 | 河南大学 | Nanometer cable transparent conducting thin film with copper inner core and preparation method thereof |
Non-Patent Citations (9)
| Title |
|---|
| BOBOMUROD HAMRAKULOV等: ""Electrodepostion Ni,Fe,Co and Cu single and multilayer nanowire arrays on anodic aluminum oxide template"", 《TRANSACTIONS OF NONFERROUS METALS SOCIETY OF CHINA》 * |
| IAN E. STEWART等: ""synthesis of Cu-Ag，Cu-Au，and Cu-Pt core-shell nanowires and their use in transparent conducting films"", 《CHEMISTRY OF MATERIALS》 * |
| M.G. CHU等: ""substrate effects on zinc deposition from zincate solution"", 《J. ELECTROCHEM. SOC.: ELECTROCHEMICAL SCIENCE AND TECHNOLOGY》 * |
| NATHAN J. GEREIN等: ""effect of ac electrodepostion conditions on the growth of high aspect ratio copper nanowires in porous aluminum oxide templates"", 《J. PHYS. CHEM. B》 * |
| YU-GUO GUO等: ""ordered Ni-Cu nanowire array with enhanced coercivity"", 《CHEM. MATER.》 * |
| 沈浩颋: ""氧化铝模板辅助生长一维纳米线阵列及其电学性质研究"", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
| 迟广俊等: ""铝阳极氧化膜模板组装铜纳米线及其TEM表征"", 《材料科学与工艺》 * |
| 郭鹤桐等: "《基础电化学及其测量》", 31 January 2009, 化学工业出版社 * |
| 马姗姗等: ""一维铜（核）-镍（壳）纳米结构的制备及其表面增强拉曼光谱"", 《物理化学学报》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107099817A (en) * | 2017-04-13 | 2017-08-29 | 合肥工业大学 | A kind of preparation method of doped ferric oxide nanometer line ordered array light anode |
| US11282620B2 (en) * | 2018-03-09 | 2022-03-22 | Ohio State Innovation Foundation | Electroplating process for connectorizing superconducting cables |
| CN110228788A (en) * | 2019-05-22 | 2019-09-13 | 湖北第二师范学院 | A kind of Berzeline nanotube and preparation method thereof, solar battery |
| CN111218702A (en) * | 2019-08-02 | 2020-06-02 | 大连理工大学 | Surface preparation method capable of preparing various nanowire structures |
| CN111218702B (en) * | 2019-08-02 | 2021-07-13 | 大连理工大学 | Surface preparation method capable of preparing various nanowire structures |
| CN110919023A (en) * | 2019-11-19 | 2020-03-27 | 吉林大学 | Method for preparing multi-dendritic platinum-based nano material by zinc ion induction |
| CN113279013A (en) * | 2021-05-24 | 2021-08-20 | 北京化工大学 | Monoatomic alloy nanowire catalyst for carbon dioxide electroreduction and preparation method thereof |
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