CN110396705B - Method for preparing nano porous silver by electrodeposition - Google Patents

Method for preparing nano porous silver by electrodeposition Download PDF

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CN110396705B
CN110396705B CN201910726447.XA CN201910726447A CN110396705B CN 110396705 B CN110396705 B CN 110396705B CN 201910726447 A CN201910726447 A CN 201910726447A CN 110396705 B CN110396705 B CN 110396705B
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silver
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copper alloy
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CN110396705A (en
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唐海宾
孟国文
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Hefei Institutes of Physical Science of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/32—Alkaline compositions
    • C23F1/40—Alkaline compositions for etching other metallic material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/006—Nanostructures, e.g. using aluminium anodic oxidation templates [AAO]
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/08—Perforated or foraminous objects, e.g. sieves
    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/64—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of silver
    • 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
    • C25D5/48—After-treatment of electroplated surfaces

Abstract

The invention discloses a method for preparing nano porous silver by electrodeposition. Firstly, respectively dripping silver nitrate solution into potassium iodide solution, stirring, mixing copper nitrate solution and sodium sulfite solution, dripping potassium iodide solution into the mixture, stirring, then adding the obtained [ AgI2]‑Complexing solution and [ CuI2]‑After the complexing solution is mixed, silver-silver chloride is used as a reference electrode, a graphite sheet is used as a counter electrode, and a conductive substrate or a conductive template is used as a working electrode and is placed in the obtained complex mixed solution for electrodeposition, then, the silver-copper alloy on the surface of the obtained conductive substrate or the conductive template with the silver-copper alloy is immersed in a saturated potassium iodide solution for cleaning, the pure silver-copper alloy on the surface of the obtained conductive substrate or the pure silver-copper alloy on the conductive film is immersed in a mixed solution of ammonia and ethanol, and oxygen is introduced into the mixed solution, so that the nano porous silver with various shapes and sizes and the pore diameter of less than or equal to 20nm is prepared. The product of the method is very easy to be widely and commercially applied to the fields of catalysis, sensors, fuel cells, SERS spectral detection and the like.

Description

Method for preparing nano porous silver by electrodeposition
Technical Field
The invention relates to a preparation method of nano porous silver, in particular to a method for preparing nano porous silver by electrodeposition.
Background
The nano-porous noble metal with large specific surface area is used as a three-dimensional continuous porous metal structure, and has important significance in the application of various technologies such as catalysis, sensors, fuel cells, Surface Enhanced Raman Scattering (SERS) spectrum detection and the like. Recently, some beneficial attempts and efforts have been made to obtain Nanoporous noble metals, such as the article entitled "Green Synthesis of Large-Scale high Ordered Core @ Shell Nanoporous Au @ Ag Nanoprod Arrays as Sensitive and Reproducible 3D SERS Substrates", ACS Appl Mater Inter, 2014, 6, 15667 ("Green Synthesis of Large area Highly Ordered Au @ Ag Core-Shell Nanorod Arrays and used as Sensitive and Reproducible three-dimensional SERS Substrates"; ACS applications and interfaces No. 6, page 15667 in 2014). The products mentioned herein are nanoporous gold nanorod arrays; it is composed ofThe preparation method comprises the following steps of2SO3、K2HPO4·3H2O and EDTA as complexing agent to prepare HAuCl4And AgNO3The complex solution is obtained by electrochemically depositing gold-silver alloy nanorods in the pore channels of the alumina template and then etching silver from the alloy structure by concentrated nitric acid. Firstly, the basis of the product is limited to nano-porous gold, compared with the noble metal nano-porous silver, the product has excellent cathode reduction performance, such as carbon dioxide electrocatalytic reduction, oxygen reduction reaction under low overpotential and the like, and higher SERS enhancement capability, and the nano-porous gold has differences in the performance and the application field in the aspects; secondly, even if the preparation method can deposit the gold-silver alloy on the surface of the conductive substrate or the conductive template with the required shape and size by an electrodeposition method for molding and obtain the product by the subsequent dealloying step, the basis of the product can only be the nano-porous gold, but the nano-porous silver can not be obtained.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a method for preparing nano porous silver by electrodeposition, wherein the pore diameter of the nano porous silver is less than or equal to 20 nm.
In order to solve the technical problem of the invention, the technical scheme adopted is that the method for preparing the nano porous silver by electrodeposition comprises an electrodeposition method and an alloy removal method, and particularly comprises the following steps:
step 1, according to the volume ratio of 20-40mmol/L silver nitrate solution to 3-5mol/L potassium iodide solution of 0.8-1.5: 1, dropping silver nitrate solution into potassium iodide solution and stirring vigorously to obtain [ AgI2]-The complexing solution of (a);
step 2, according to the volume ratio of 0.1-0.3mol/L copper nitrate solution, 0.5-0.7mol/L sodium sulfite solution and 3-6mol/L potassium iodide solution being 0.3-0.5: 0.5-0.7: 1, mixing the two, dripping into potassium iodide solution, and stirring vigorously to obtain [ CuI2]-The complexing solution of (a);
step 3, according to [ AgI2]-And [ CuI ] and2]-the volume ratio of the complexing solution is 0.8-1.5: 1, mixing the two solutions to obtain a complex mixed solution;
step 4, putting silver-silver chloride serving as a reference electrode, a graphite sheet serving as a counter electrode and a conductive substrate or a conductive template serving as a working electrode into a complex mixed solution, and carrying out electrodeposition for at least 5min under the voltage of the working electrode relative to the reference electrode- (0.5-0.7) V to obtain a silver-copper alloy on the surface of the conductive substrate or in the conductive template;
step 5, immersing the silver-copper alloy on the surface of the conductive substrate into a saturated potassium iodide solution for cleaning to obtain pure silver-copper alloy on the surface of the conductive substrate, or immersing the conductive template provided with the silver-copper alloy into a saturated potassium iodide solution for cleaning, then bonding the conductive film of the conductive template with the metal which is active than copper by using a conductive adhesive tape, then placing the conductive template in an alkaline solution for corroding the template, then removing the conductive adhesive tape and the metal which is active than copper, and obtaining pure silver-copper alloy on the conductive film;
and 6, immersing the pure silver-copper alloy on the surface of the conductive substrate or the pure silver-copper alloy on the conductive film into the solution according to the volume ratio of 25-28 wt% of ammonia water to ethanol of 0.8-1.5: 1, and introducing oxygen into the mixed solution for at least 40min to prepare the nano porous silver film, the nano porous silver nanowire, the nano porous silver nanorod array or the nano porous silver microsphere array, wherein the pore diameter of the nano porous silver film is less than or equal to 20 nm.
As a further improvement of the method for preparing nano-porous silver by electrodeposition:
preferably, the conductive substrate is indium tin oxide conductive glass, or fluorine-doped tin oxide conductive glass, or a silicon wafer.
Preferably, the conductive template is an alumina template with a conductive film, or a polystyrene bead template with a conductive film, or a template obtained on the surface of indium tin oxide conductive glass or fluorine-doped tin oxide conductive glass or a silicon wafer by using a photoetching or electron beam etching method.
Preferably, the distance between the reference electrode and the working electrode in the complex mixed solution is 0.2-2cm, and the distance between the counter electrode and the working electrode is 2-8 cm.
Preferably, the thickness of the conductive film of the conductive template is more than or equal to 150 nm.
Preferably, the metal active with respect to copper is metallic zinc, or metallic aluminum, or metallic magnesium, or metallic iron.
Preferably, the silver-copper alloy on the surface of the conductive substrate or the conductive template provided with the silver-copper alloy is soaked in a saturated potassium iodide solution for cleaning, and then is cleaned by using deionized water.
Preferably, the alkali solution is a sodium hydroxide solution, or a potassium hydroxide solution, or a lithium hydroxide solution.
Compared with the prior art, the beneficial effects are that:
firstly, respectively characterizing the prepared product by using a scanning electron microscope and an X-ray energy spectrometer, and obtaining the product which is a nano porous silver film, a nano porous silver nanowire, a nano porous silver nanorod array or a nano porous silver microsphere array by combining the results with the preparation method; wherein the diameter of the nanometer porous silver is less than or equal to 20 nm. The product assembled by the nano-porous silver is not only due to the performance and the characteristics of the noble metal nano-silver, but also due to the huge specific surface area of the nano-porous silver; and products with various appearances are constructed on the basis of the nano porous silver, so that the performance and the application field of the products are greatly expanded.
Secondly, the preparation method not only prepares the product with the pore diameter of the nano-porous silver of any shape and size less than or equal to 20 nm; and stable silver-copper metal ion complexing solution is obtained, so that the silver-copper metal ion complexing solution can simultaneously perform cathodic reduction besides having a relatively standard reduction potential, and the mechanism is realized as follows: firstly, high-concentration iodine ions complex silver ions to form a stable complex [ AgI2]-Secondly, the Cu is treated by sodium sulfite2+ reduction to Cu +, followed by high concentration of iodide ion complexing the Cu +, forming a stable complex [ CuI ]2]-Thirdly, the stability constants of the two metal complexes are larger and are respectively 11.7 and 8.8, so that the two metal complexes can form stable mixed solution, and fourthly[AgI2]-Has a standard reduction potential of-0.152V, and [ CuI ]2]-The standard reduction potential of the silver-copper alloy is equivalent to-0.182V, and the cathode reduction can be simultaneously carried out on the electrode, so that the electrochemical codeposition is realized, and the silver-copper alloy is formed; the preparation method has the characteristics of convenient control of the preparation process and low cost of raw materials; further, the product is easy to be widely applied to the fields of catalysis, sensors, fuel cells, surface enhanced Raman scattering spectrum detection and the like in a commercial mode.
Drawings
Fig. 1 is one of results of characterization of the silver-copper alloy obtained during the preparation process and the nano-porous silver nanowires obtained as a product using a Scanning Electron Microscope (SEM) and an X-ray energy spectrometer, respectively. Wherein, a in figure 1 is SEM image of silver-copper alloy nanowire; b, an X-ray energy spectrum of the silver-copper alloy nanowire shown in the diagram a is shown, and the insets in the diagram are distribution diagrams of two elements in the nanowire; c is SEM image of the nano-porous silver nanowire formed after the silver-copper alloy nanowire shown in the a is de-alloyed; d is the high magnification SEM image of c; and e is the X-ray energy spectrum analysis diagram of the nano-porous silver nanowire shown in the c.
FIG. 2 is one of the results of characterization of the silver-copper alloy obtained during the preparation process and the prepared product, namely the nano-porous silver nanorod array, using a scanning electron microscope. Wherein, a in FIG. 2 is SEM image of silver-copper alloy nanorod array; and b, the image is an SEM image of the nano-porous silver nanorod array formed after the silver-copper alloy nanorod array shown in the image a is de-alloyed.
FIG. 3 shows the results of the characterization of the silver-copper alloy obtained during the preparation process and the prepared product, namely the nano-porous silver microsphere array, by using a scanning electron microscope. Wherein, a in fig. 3 is an SEM image of the silver-copper alloy microsphere array; and b, the image is an SEM image of the nano-porous silver microsphere array formed after the silver-copper alloy microsphere array shown in the image a is de-alloyed, and the inset in the upper right corner of the image is the high-magnification SEM image of the nano-porous silver microsphere array.
Detailed Description
Preferred embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.
First commercially available or manufactured on its own:
silver nitrate solution;
a potassium iodide solution;
copper nitrate solution;
sodium sulfite solution;
indium tin oxide conductive glass, fluorine-doped tin oxide conductive glass and a silicon wafer which are used as conductive substrates;
an alumina template with a conductive film as a conductive template, a polystyrene bead template with a conductive film and a template obtained on the surface of indium tin oxide conductive glass or fluorine-doped tin oxide conductive glass or a silicon wafer by using a photoetching or electron beam etching method;
metallic zinc, metallic aluminum, metallic magnesium and metallic iron as metals active against copper;
deionized water;
sodium hydroxide solution, potassium hydroxide solution and lithium hydroxide solution as alkali solutions;
ammonia water;
and (3) ethanol.
Then:
example 1
The preparation method comprises the following specific steps:
step 1, according to the volume ratio of 20mmol/L silver nitrate solution to 5mol/L potassium iodide solution of 0.8: 1, dropping silver nitrate solution into potassium iodide solution and stirring vigorously to obtain [ AgI2]-The complexing solution of (1).
Step 2, according to the volume ratio of 0.1mol/L copper nitrate solution, 0.7mol/L sodium sulfite solution and 3mol/L potassium iodide solution being 0.3: 0.7: 1, mixing the two, dripping into potassium iodide solution, and stirring vigorously to obtain [ CuI2]-The complexing solution of (1).
Step 3, according to [ AgI2]-And [ CuI ] and2]-the volume ratio of the complex solution of (2) is 0.8: 1, and mixing the two solutions to obtain a complex mixed solution.
Step 4, putting silver-silver chloride serving as a reference electrode, a graphite sheet serving as a counter electrode and a conductive substrate or a conductive template serving as a working electrode into a complex mixed solution together, and performing electrodeposition for 45min under the voltage of the working electrode at-0.5V relative to the reference electrode; the conductive substrate is indium tin oxide conductive glass, the conductive template is an aluminum oxide template with a conductive film, the distance between a reference electrode and a working electrode in a complex mixed solution is 0.2cm, the distance between a counter electrode and the working electrode is 8cm, and the silver-copper alloy is obtained on the surface of the conductive substrate or in the conductive template.
Step 5, immersing the silver-copper alloy on the surface of the conductive substrate into a saturated potassium iodide solution for cleaning, and then cleaning the silver-copper alloy by using deionized water to obtain pure silver-copper alloy on the surface of the conductive substrate; or immersing the conductive template provided with the silver-copper alloy into a saturated potassium iodide solution for cleaning, cleaning the conductive template by using deionized water, bonding the conductive film of the conductive template with the metal which is active than copper by using a conductive adhesive tape, then placing the bonded conductive film and the metal which is active than copper into an aqueous alkali to corrode the template, and then removing the conductive adhesive tape and the metal which is active than copper, wherein the thickness of the conductive film of the conductive template is 150nm, the metal which is active than copper is zinc, and the aqueous alkali is a sodium hydroxide solution, so that pure silver-copper alloy is obtained on the conductive film.
And 6, immersing the pure silver-copper alloy on the surface of the conductive substrate or the pure silver-copper alloy on the conductive film into 25 wt% of ammonia water and ethanol according to the volume ratio of 1.5: 1, and introducing oxygen into the mixed solution for 40min to obtain the nano porous silver film with the pore diameter of less than or equal to 20nm or the nano porous silver nanowire with the pore diameter of less than or equal to 20nm, which is similar to that shown in figure 1d, and is shown by the curve in figure 1 e.
Example 2
The preparation method comprises the following specific steps:
step 1, according to the volume ratio of 25mmol/L silver nitrate solution to 4.5mol/L potassium iodide solution of 0.98: 1, dropping silver nitrate solution into potassium iodide solution and stirring vigorously to obtain [ AgI2]-The complexing solution of (1).
Step 2, according to 0.15mol/L copper nitrate solution, 0.65mol/L sodium sulfite solution and 3.8mol/L potassium iodide solutionIs 0.35: 0.65: 1, mixing the two, dripping into potassium iodide solution, and stirring vigorously to obtain [ CuI2]-The complexing solution of (1).
Step 3, according to [ AgI2]-And [ CuI ] and2]-the volume ratio of the complex solution of (2) is 0.98: 1, and mixing the two solutions to obtain a complex mixed solution.
Step 4, putting the silver-silver chloride serving as a reference electrode, the graphite flake serving as a counter electrode and the conductive substrate or the conductive template serving as a working electrode into a complex mixed solution, and performing electrodeposition for 35min under the voltage of the working electrode relative to the reference electrode, which is-0.55V; the conductive substrate is indium tin oxide conductive glass, the conductive template is an aluminum oxide template with a conductive film, the distance between a reference electrode and a working electrode in a complex mixed solution is 0.7cm, the distance between a counter electrode and the working electrode is 6.5cm, and the silver-copper alloy is obtained on the surface of the conductive substrate or in the conductive template.
Step 5, immersing the silver-copper alloy on the surface of the conductive substrate into a saturated potassium iodide solution for cleaning, and then cleaning the silver-copper alloy by using deionized water to obtain pure silver-copper alloy on the surface of the conductive substrate; or immersing the conductive template provided with the silver-copper alloy into a saturated potassium iodide solution for cleaning, cleaning the conductive template by using deionized water, bonding the conductive film of the conductive template with the metal which is active compared with copper by using a conductive adhesive tape, then placing the bonded conductive film and the metal which is active compared with copper into an aqueous alkali to corrode the template, and then removing the conductive adhesive tape and the metal which is active compared with copper, wherein the thickness of the conductive film of the conductive template is 180nm, the metal which is active compared with copper is metal zinc, and the aqueous alkali is a sodium hydroxide solution, so that pure silver-copper alloy is obtained on the conductive film.
And 6, immersing the pure silver-copper alloy on the surface of the conductive substrate or the pure silver-copper alloy on the conductive film into the solution prepared by mixing 25.8 wt% of ammonia water and ethanol according to a volume ratio of 1.33: 1, and introducing oxygen for 45min to obtain a nano-porous silver film with the pore diameter of less than or equal to 20nm or a nano-porous silver nanowire with the pore diameter of less than or equal to 20nm, which is similar to that shown in figure 1d, and is shown by the curve in figure 1 e.
Example 3
The preparation method comprises the following specific steps:
step 1, according to the volume ratio of 30mmol/L silver nitrate solution to 4mol/L potassium iodide solution of 1.16: 1, dropping silver nitrate solution into potassium iodide solution and stirring vigorously to obtain [ AgI2]-The complexing solution of (1).
Step 2, according to the volume ratio of 0.2mol/L copper nitrate solution, 0.6mol/L sodium sulfite solution and 4.5mol/L potassium iodide solution being 0.4: 0.6: 1, mixing the two, dripping into potassium iodide solution, and stirring vigorously to obtain [ CuI2]-The complexing solution of (1).
Step 3, according to [ AgI2]-And [ CuI ] and2]-the volume ratio of the complexing solution (b) is 1.16: 1, and mixing the two solutions to obtain a complex mixed solution.
Step 4, putting the silver-silver chloride serving as a reference electrode, the graphite flake serving as a counter electrode and the conductive substrate or the conductive template serving as a working electrode into a complex mixed solution, and performing electrodeposition for 25min under the voltage of the working electrode relative to the reference electrode, which is-0.6V; the conductive substrate is indium tin oxide conductive glass, the conductive template is an aluminum oxide template with a conductive film, the distance between a reference electrode and a working electrode in a complex mixed solution is 1.1cm, the distance between a counter electrode and the working electrode is 5cm, and the silver-copper alloy is obtained on the surface of the conductive substrate or in the conductive template.
Step 5, immersing the silver-copper alloy on the surface of the conductive substrate into a saturated potassium iodide solution for cleaning, and then cleaning the silver-copper alloy by using deionized water to obtain pure silver-copper alloy on the surface of the conductive substrate; or immersing the conductive template provided with the silver-copper alloy into a saturated potassium iodide solution for cleaning, cleaning the conductive template by using deionized water, bonding the conductive film of the conductive template with the metal which is active than copper by using a conductive adhesive tape, then placing the bonded conductive film and the metal which is active than copper into an aqueous alkali to corrode the template, and then removing the conductive adhesive tape and the metal which is active than copper, wherein the thickness of the conductive film of the conductive template is 200nm, the metal which is active than copper is zinc, and the aqueous alkali is a sodium hydroxide solution, so that pure silver-copper alloy is obtained on the conductive film.
And 6, immersing the pure silver-copper alloy on the surface of the conductive substrate or the pure silver-copper alloy on the conductive film into the solution prepared by mixing 26.5 wt% of ammonia water and ethanol according to a volume ratio of 1.16: 1, and introducing oxygen for 50min to obtain a nano-porous silver film with a pore diameter of less than or equal to 20nm or a nano-porous silver nanowire with a pore diameter of less than or equal to 20nm as shown in fig. 1d and a nano-porous silver nanowire with a pore diameter of less than or equal to 20nm as shown in a curve in fig. 1 e.
Example 4
The preparation method comprises the following specific steps:
step 1, according to the volume ratio of 35mmol/L silver nitrate solution to 3.5mol/L potassium iodide solution of 1.33: 1, dropping silver nitrate solution into potassium iodide solution and stirring vigorously to obtain [ AgI2]-The complexing solution of (1).
Step 2, according to the volume ratio of 0.25mol/L copper nitrate solution, 0.55mol/L sodium sulfite solution and 5.3mol/L potassium iodide solution being 0.45: 0.55: 1, mixing the two, dripping into potassium iodide solution, and stirring vigorously to obtain [ CuI2]-The complexing solution of (1).
Step 3, according to [ AgI2]-And [ CuI ] and2]-the volume ratio of the complexing solution (b) is 1.33: 1, and mixing the two solutions to obtain a complex mixed solution.
Step 4, putting the silver-silver chloride serving as a reference electrode, the graphite flake serving as a counter electrode and the conductive substrate or the conductive template serving as a working electrode into a complex mixed solution, and performing electrodeposition for 15min under the voltage of the working electrode relative to the reference electrode of-0.65V; the conductive substrate is indium tin oxide conductive glass, the conductive template is an aluminum oxide template with a conductive film, the distance between a reference electrode and a working electrode in a complex mixed solution is 1.5cm, the distance between a counter electrode and the working electrode is 3.5cm, and the silver-copper alloy is obtained on the surface of the conductive substrate or in the conductive template.
Step 5, immersing the silver-copper alloy on the surface of the conductive substrate into a saturated potassium iodide solution for cleaning, and then cleaning the silver-copper alloy by using deionized water to obtain pure silver-copper alloy on the surface of the conductive substrate; or immersing the conductive template provided with the silver-copper alloy into a saturated potassium iodide solution for cleaning, cleaning the conductive template by using deionized water, bonding the conductive film of the conductive template with the metal which is active than copper by using a conductive adhesive tape, then placing the bonded conductive film and the metal which is active than copper into an aqueous alkali to corrode the template, and then removing the conductive adhesive tape and the metal which is active than copper, wherein the thickness of the conductive film of the conductive template is 230nm, the metal which is active than copper is zinc, and the aqueous alkali is a sodium hydroxide solution, so that pure silver-copper alloy is obtained on the conductive film.
And 6, immersing the pure silver-copper alloy on the surface of the conductive substrate or the pure silver-copper alloy on the conductive film into the solution according to the volume ratio of 27.3 wt% of ammonia water to ethanol of 0.98: 1, and introducing oxygen into the mixed solution for 55min to obtain the nano-porous silver film with the pore diameter of less than or equal to 20nm or the nano-porous silver nanowire with the pore diameter of less than or equal to 20nm, which is similar to that shown in figure 1d, and is shown by the curve in figure 1 e.
Example 5
The preparation method comprises the following specific steps:
step 1, according to the volume ratio of 40mmol/L silver nitrate solution to 3mol/L potassium iodide solution of 1.5: 1, dropping silver nitrate solution into potassium iodide solution and stirring vigorously to obtain [ AgI2]-The complexing solution of (1).
Step 2, according to the volume ratio of 0.3mol/L copper nitrate solution, 0.5mol/L sodium sulfite solution and 6mol/L potassium iodide solution being 0.5: 0.5: 1, mixing the two, dripping into potassium iodide solution, and stirring vigorously to obtain [ CuI2]-The complexing solution of (1).
Step 3, according to [ AgI2]-And [ CuI ] and2]-the volume ratio of the complexing solution of (a) is 1.5: 1, and mixing the two solutions to obtain a complex mixed solution.
Step 4, putting the silver-silver chloride serving as a reference electrode, the graphite flake serving as a counter electrode and the conductive substrate or the conductive template serving as a working electrode into a complex mixed solution, and performing electrodeposition for 5min under the voltage of the working electrode relative to the reference electrode, which is-0.7V; the conductive substrate is indium tin oxide conductive glass, the conductive template is an aluminum oxide template with a conductive film, the distance between a reference electrode and a working electrode in a complex mixed solution is 2cm, the distance between a counter electrode and the working electrode is 2cm, and the silver-copper alloy is obtained on the surface of the conductive substrate or in the conductive template.
Step 5, immersing the silver-copper alloy on the surface of the conductive substrate into a saturated potassium iodide solution for cleaning, and then cleaning the silver-copper alloy by using deionized water to obtain pure silver-copper alloy on the surface of the conductive substrate; or immersing the conductive template provided with the silver-copper alloy into a saturated potassium iodide solution for cleaning, cleaning the conductive template by using deionized water, bonding the conductive film of the conductive template with the metal which is active than copper by using a conductive adhesive tape, then placing the bonded conductive film and the metal which is active than copper into an aqueous alkali to corrode the template, and then removing the conductive adhesive tape and the metal which is active than copper, wherein the thickness of the conductive film of the conductive template is 250nm, the metal which is active than copper is zinc, and the aqueous alkali is a sodium hydroxide solution, so that pure silver-copper alloy is obtained on the conductive film.
And 6, immersing the pure silver-copper alloy on the surface of the conductive substrate or the pure silver-copper alloy on the conductive film into the solution according to the volume ratio of 28 wt% ammonia water to ethanol of 0.8: 1, and introducing oxygen for 60min to obtain a nano-porous silver film with the pore diameter of less than or equal to 20nm or a nano-porous silver nanowire with the pore diameter of less than or equal to 20nm, which is similar to that shown in figure 1d, and is shown by the curve in figure 1 e.
Then, indium tin oxide conductive glass or fluorine-doped tin oxide conductive glass or silicon wafer as a conductive substrate, an aluminum oxide template with a conductive film or a polystyrene bead template with a conductive film as a conductive template or a template obtained on the surface of the indium tin oxide conductive glass or fluorine-doped tin oxide conductive glass or silicon wafer by using a photoetching or electron beam etching method, metallic zinc or metallic aluminum or metallic magnesium or metallic iron as a metal which is more reactive than copper, and a sodium hydroxide solution or a potassium hydroxide solution or a lithium hydroxide solution as an alkali solution are respectively selected, the above-mentioned examples 1 to 5 are repeated, and a nano porous silver film, or a nano porous silver nanowire, or a nano porous silver nanorod array, of which the pore diameter of the nano porous silver is less than or equal to 20nm as shown in fig. 1d, fig. 2b and fig. 3b and as shown by the curve in fig. 1e, are similarly prepared, or a nanoporous silver microsphere array.
It is apparent that those skilled in the art can make various modifications and variations to the method for preparing nanoporous silver by electrodeposition of the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is intended to include such modifications and variations.

Claims (8)

1. A method for preparing nano-porous silver by electrodeposition comprises an electrodeposition method and an alloy removal method, and is characterized by comprising the following steps:
step 1, according to the volume ratio of 20-40mmol/L silver nitrate solution to 3-5mol/L potassium iodide solution of 0.8-1.5: 1, dropping silver nitrate solution into potassium iodide solution and stirring vigorously to obtain [ AgI2]-The complexing solution of (a);
step 2, according to the volume ratio of 0.1-0.3mol/L copper nitrate solution, 0.5-0.7mol/L sodium sulfite solution and 3-6mol/L potassium iodide solution being 0.3-0.5: 0.5-0.7: 1, mixing the two, dripping into potassium iodide solution, and stirring vigorously to obtain [ CuI2]-The complexing solution of (a);
step 3, according to [ AgI2]-And [ CuI ] and2]-the volume ratio of the complexing solution is 0.8-1.5: 1, mixing the two solutions to obtain a complex mixed solution;
step 4, putting silver-silver chloride serving as a reference electrode, a graphite sheet serving as a counter electrode and a conductive substrate or a conductive template serving as a working electrode into a complex mixed solution, and carrying out electrodeposition for at least 5min under the voltage of the working electrode relative to the reference electrode- (0.5-0.7) V to obtain a silver-copper alloy on the surface of the conductive substrate or in the conductive template;
step 5, immersing the silver-copper alloy on the surface of the conductive substrate into a saturated potassium iodide solution for cleaning to obtain pure silver-copper alloy on the surface of the conductive substrate, or immersing the conductive template provided with the silver-copper alloy into a saturated potassium iodide solution for cleaning, then bonding the conductive film of the conductive template with the metal which is active than copper by using a conductive adhesive tape, then placing the conductive template in an alkaline solution for corroding the template, then removing the conductive adhesive tape and the metal which is active than copper, and obtaining pure silver-copper alloy on the conductive film;
and 6, immersing the pure silver-copper alloy on the surface of the conductive substrate or the pure silver-copper alloy on the conductive film into the solution according to the volume ratio of 25-28 wt% of ammonia water to ethanol of 0.8-1.5: 1, and introducing oxygen into the mixed solution for at least 40min to prepare the nano porous silver film, the nano porous silver nanowire, the nano porous silver nanorod array or the nano porous silver microsphere array, wherein the pore diameter of the nano porous silver film is less than or equal to 20 nm.
2. The method for preparing nano-porous silver by electrodeposition as claimed in claim 1, wherein the conductive substrate is indium tin oxide conductive glass, or fluorine-doped tin oxide conductive glass, or a silicon wafer.
3. The method for preparing nano-porous silver by electrodeposition as claimed in claim 1, wherein the conductive template is an alumina template with a conductive film, or a polystyrene bead template with a conductive film, or a template obtained on the surface of indium tin oxide conductive glass or fluorine-doped tin oxide conductive glass or a silicon wafer by using a photolithography or electron beam etching method.
4. The method for preparing nanoporous silver by electrodeposition as claimed in claim 1, wherein the distance between the reference electrode and the working electrode placed in the complex mixed solution is 0.2-2cm, and the distance between the counter electrode and the working electrode is 2-8 cm.
5. The method for preparing nano-porous silver by electrodeposition as claimed in claim 1, wherein the thickness of the conductive film of the conductive template is not less than 150 nm.
6. The method for preparing nano-porous silver by electrodeposition as claimed in claim 1, wherein the metal that is reactive to copper is metallic zinc, or metallic aluminum, or metallic magnesium, or metallic iron.
7. The method for preparing nano-porous silver by electrodeposition as claimed in claim 1, wherein the silver-copper alloy or the conductive template provided with the silver-copper alloy on the surface of the conductive substrate is washed by immersing it in a saturated potassium iodide solution and then washing it with deionized water.
8. The method for preparing nano-porous silver by electrodeposition as claimed in claim 1, wherein the alkali solution is a sodium hydroxide solution, or a potassium hydroxide solution, or a lithium hydroxide solution.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3914161A (en) * 1972-06-16 1975-10-21 Matsushita Electric Ind Co Ltd Electroplating solutions for depositing silver alloys and a method of forming silver alloys by electroplating
WO2004001101A2 (en) * 2002-06-24 2003-12-31 Politecnico Di Milano Electrolytic bath for the electrodeposition of noble metals and their alloys
CN102443823A (en) * 2010-10-13 2012-05-09 周宏霞 Foamed copper-silver alloy material and its preparation method
CN103058132A (en) * 2012-12-26 2013-04-24 中国科学院合肥物质科学研究院 Ordered porous gold nanorod array and preparation method and application thereof
CN103303861A (en) * 2013-05-14 2013-09-18 中国科学院上海硅酸盐研究所 Three-dimensional ordered precious metal nanotube array electrode and preparation method thereof
CN105112958A (en) * 2015-08-25 2015-12-02 中山大学 Method for obtaining nano-porous silver in base-material-loaded dealloying mode

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54141346A (en) * 1978-04-26 1979-11-02 Matsushita Electric Ind Co Ltd Silver-copper alloy plating method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3914161A (en) * 1972-06-16 1975-10-21 Matsushita Electric Ind Co Ltd Electroplating solutions for depositing silver alloys and a method of forming silver alloys by electroplating
WO2004001101A2 (en) * 2002-06-24 2003-12-31 Politecnico Di Milano Electrolytic bath for the electrodeposition of noble metals and their alloys
CN102443823A (en) * 2010-10-13 2012-05-09 周宏霞 Foamed copper-silver alloy material and its preparation method
CN103058132A (en) * 2012-12-26 2013-04-24 中国科学院合肥物质科学研究院 Ordered porous gold nanorod array and preparation method and application thereof
CN103303861A (en) * 2013-05-14 2013-09-18 中国科学院上海硅酸盐研究所 Three-dimensional ordered precious metal nanotube array electrode and preparation method thereof
CN105112958A (en) * 2015-08-25 2015-12-02 中山大学 Method for obtaining nano-porous silver in base-material-loaded dealloying mode

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