CN110396705A - The method of the porous silver of electrodeposited nanocrystalline - Google Patents
The method of the porous silver of electrodeposited nanocrystalline Download PDFInfo
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Abstract
The invention discloses a kind of methods of the porous silver of electrodeposited nanocrystalline.Silver nitrate solution is first instilled after liquor kalii iodide stirring, copper nitrate solution and sodium sulfite solution mix respectively and instills liquor kalii iodide stirring, the then [AgI that will be obtained by it2]‑Complex solution and [CuI2]‑After complex solution mixing, using silver-silver chloride as reference electrode, graphite flake is to electrode, electro-deposition in the complex compound mixed solution that conductive substrates or conductive template are placed in for working electrode, then, first by the yellow gold on obtained conductive substrates surface or be equipped with yellow gold conductive template immerse saturated solution of potassium iodide in clean, yellow gold pure on obtained conductive substrates surface pure yellow gold or conductive film is immersed again in the mixed solution of ammonium hydroxide and ethyl alcohol, and it is passed through oxygen thereto, the nano-porous silver of the various appearance and sizes of bore dia≤20nm is made.Its product be extremely easy to widely commercial applications in catalysis, sensor, fuel cell and SERS spectra detection etc. fields.
Description
Technical field
The present invention relates to a kind of preparation method of nano-porous silver, the side of especially a kind of porous silver of electrodeposited nanocrystalline
Method.
Background technique
Nanoporous noble metal with bigger serface as a kind of metal structure that three-dimensional is continuous poriferous, catalysis,
There is important meaning in the application of the multiple technologies such as sensor, fuel cell and Surface enhanced Raman scattering (SERS) spectral detection
Justice.In the recent period, people have made some good tries and effort, such as entitled " Green to obtain nanoporous noble metal
Synthesis of Large-Scale Highly Ordered Core@Shell Nanoporous Au@Ag Nanorod
Arrays as Sensitive and Reproducible 3D SERS Substrates ", ACS Appl Mater
Inter, 2014,6,15667 (" green syt of the Au@Ag core-shell nanometer rod array of large area high-sequential and be used as it is sensitive and
Repeatable three-dimensional S ERS substrate ", " ACS application material and interface " the 6th phase page 15667 in 2014) article.It is mentioned in this article
And product be nanoporous gold nano stick array；Preparation method is with Na2SO3、K2HPO4·3H2O and EDTA is complexing agent, is matched
Set HAuCl4And AgNO3Complex solution, after the electrochemical deposition electrum nanometer rods in the duct of alumina formwork,
Silver is etched from alloy structure with concentrated nitric acid to obtain product.Though this product can be used as sensitive and repeatable three-dimensional S ERS lining
Bottom, but all there is shortcomings with preparation method, firstly, the basis of product is limited as nano-porous gold, in contrast, together
Excellent cathodic reduction performance possessed by nano-porous silver for noble metal --- carbon dioxide electro-catalysis reduction, low overpotential
Under oxygen reduction reaction etc. and higher SERS enhance ability, and nano-porous gold is in the performance and application neck of above-mentioned aspect
All there is gap in domain；Secondly, electrum can be deposited on conductive substrates surface or institute by electrodeposition process by preparation method
It needs to be formed in the conductive template of morphology and size, and obtains product in subsequent removal alloying step, its right product
Basis can only be nano-porous gold, and cannot get nano-porous silver.
Summary of the invention
The technical problem to be solved in the present invention place in order to overcome the shortcomings in the prior art, provides a kind of nano-porous silver
The method of the porous silver of bore dia≤20nm electrodeposited nanocrystalline.
To solve technical problem of the invention, used technical solution is the method for the porous silver of electrodeposited nanocrystalline
It is made of electrodeposition process and removal alloyage, especially steps are as follows for completion:
It step 1, is 0.8- according to the volume ratio of the silver nitrate solution of 20-40mmol/L and the liquor kalii iodide of 3-5mol/L
Silver nitrate solution is instilled in liquor kalii iodide and is vigorously stirred, obtains [AgI by the ratio of 1.5:12]-Complex solution；
Step 2, according to the copper nitrate solution of 0.1-0.3mol/L, the sodium sulfite solution and 3- of 0.5-0.7mol/L
The volume ratio of the liquor kalii iodide of 6mol/L is the ratio of 0.3-0.5:0.5-0.7:1, instills potassium iodide after the above two are mixed
It in solution and is vigorously stirred, obtains [CuI2]-Complex solution；
Step 3, according to [AgI2]-Complex solution and [CuI2]-Complex solution volume ratio be 0.8-1.5:1 ratio
Example, the two is mixed, complex compound mixed solution is obtained；
It step 4, be to electrode, conductive substrates or conductive template as reference electrode, graphite flake using silver-silver chloride is work electricity
Pole is placed in together in complex compound mixed solution, the electro-deposition under working electrode is relative to the voltage of reference electrode-(0.5-0.7) V
At least 5min obtains yellow gold in conductive substrates surface or conductive template；
Step 5, the yellow gold on conductive substrates surface is immersed in saturated solution of potassium iodide and is cleaned, in conductive substrates surface
Pure yellow gold is obtained, or the conductive template for being equipped with yellow gold is immersed in saturated solution of potassium iodide after cleaning, is used
The conductive film of conductive template is placed in aqueous slkali with the metal bonding sprinkled than work in copper and erodes template by conductive tape, later,
The metal for removing conductive tape and being sprinkled than work in copper, in obtaining pure yellow gold on conductive film；
Step 6, yellow gold pure on conductive substrates surface pure yellow gold or conductive film is immersed according to 25-
In the mixed solution that the ratio that the ammonium hydroxide of 28wt% and the volume ratio of ethyl alcohol are 0.8-1.5:1 is prepared, and it is passed through oxygen thereto
Bore dia≤20nm nanoporous the Ag films or nanoporous silver nanowires of nano-porous silver are made at least 40min, or
Nano-porous silver nanometer stick array or nanoporous silver micron ball array.
Further improvements in methods as the porous silver of electrodeposited nanocrystalline:
Preferably, conductive substrates are indium tin oxide-coated glass or fluorine-doped tin oxide electro-conductive glass or silicon wafer.
Preferably, conductive template is the alumina formwork with conductive film, or the polystyrene sphere mould with conductive film
Plate, or using photoetching or electron beam lithography method in indium tin oxide-coated glass or fluorine-doped tin oxide electro-conductive glass or silicon wafer
The template that surface obtains.
Preferably, the spacing of the reference electrode and working electrode that are placed in complex compound mixed solution is 0.2-2cm, to electrode
Spacing with working electrode is 2-8cm.
Preferably, thickness >=150nm of the conductive film of conductive template.
It preferably, is metallic zinc or metallic aluminium or magnesium metal or metallic iron than the metal that work in copper sprinkle.
Preferably, by the yellow gold on conductive substrates surface or be equipped with yellow gold conductive template immerse saturation potassium iodide
After being cleaned in solution, it is cleaned using deionized water.
Preferably, aqueous slkali is sodium hydroxide solution or potassium hydroxide solution or lithium hydroxide solution.
Beneficial effect compared with the existing technology is:
First, being characterized respectively using scanning electron microscope and X-ray energy spectrometer to product obtained, by its result and combine
Preparation method it is found that product is nanoporous Ag films or nanoporous silver nanowires or nano-porous silver nanometer stick array,
Or nanoporous silver micron ball array；Bore dia≤20nm of nano-porous silver therein.It is this to be assembled by nano-porous silver
Product, not only due to the performance and speciality of noble metal nano silver, but also because of the huge specific surface area of nano-porous silver；Due also to receive
The product for the various patterns being built into based on meter Duo Kong silver, and it is greatly expanded the performance and application field of product.
Second, bore dia≤20nm of the nano-porous silver of any pattern and size has not only been made in preparation method
Product；Stable silver-bearing copper complexing of metal ion solution is had also obtained, makes it other than with comparable standard electrode potential,
Cathodic reduction can occur simultaneously, the mechanism realized are as follows: first is that silver ion has been complexed in the iodide ion of high concentration, form stable
Complex compound [AgI2]-, second is that sodium sulfite is by Cu2+ it is reduced to Cu+, Cu+ is complexed the iodide ion for the high concentration being added later, shape
At stable complex compound [CuI2]-, third is that the stability constant of two kinds of metal complexes is larger, respectively 11.7 and 8.8, it is ensured that
The two is capable of forming stable mixed solution, fourth is that [AgI2]-Standard electrode potential be -0.152V, with [CuI2]-Mark
Quasi- reduction potential -0.182V is suitable, and cathodic reduction can occur on the electrode simultaneously, realize electrochemical co-deposition, form silver-bearing copper
Alloy；More have the characteristics that manufacturing process is inexpensive convenient for control, raw material；And then make product be extremely easy to widely commercial applications in
The fields such as catalysis, sensor, fuel cell and Surface Enhanced Raman Scattering Spectrum detection.
Detailed description of the invention
Fig. 1 be to obtained in preparation process yellow gold and product obtained --- nanoporous silver nanowires makes respectively
One of the result characterized with scanning electron microscope (SEM) and X-ray energy spectrometer.Wherein, a figure in Fig. 1 is yellow gold nanometer
The SEM image of line；B figure is the X-ray energy spectrogram of yellow gold nano wire shown in a schemes, and the illustration in figure is that two kinds of elements are being received
Distribution map in rice noodles；C figure is that a schemes the nanoporous silver nanowires formed after shown yellow gold nano wire removal alloying
SEM image；D figure is the high magnification SEM image of c figure；E figure is the X-ray energy spectrum analysis of nanoporous silver nanowires shown in c schemes
Figure.
Fig. 2 be to obtained in preparation process yellow gold and product obtained --- nano-porous silver nanometer stick array makes
One of the result characterized with scanning electron microscope.Wherein, a figure in Fig. 2 is the SEM image of yellow gold nanometer stick array；B figure
For the SEM image of a nano-porous silver nanometer stick array for scheming to be formed after shown yellow gold nanometer stick array removal alloying.
Fig. 3 is to the yellow gold and product obtained obtained in preparation process --- nanoporous silver micron ball array makes
One of the result characterized with scanning electron microscope.Wherein, a figure in Fig. 3 is the SEM image of yellow gold micron ball array；B figure
For the SEM image of a nanoporous silver micron ball array for scheming to be formed after shown yellow gold micron ball array removal alloying, the figure right side
The illustration at upper angle is its powerful SEM image.
Specific embodiment
Preferred embodiment of the invention is described in further detail with reference to the accompanying drawing.
It buys from market or is voluntarily made first:
Silver nitrate solution；
Liquor kalii iodide；
Copper nitrate solution；
Sodium sulfite solution；
Indium tin oxide-coated glass, fluorine-doped tin oxide electro-conductive glass and silicon wafer as conductive substrates；
As the alumina formwork with conductive film of conductive template, the polystyrene sphere template with conductive film and make
It is obtained with the method for photoetching or electron beam lithography in the surface of indium tin oxide-coated glass or fluorine-doped tin oxide electro-conductive glass or silicon wafer
The template obtained；
Metallic zinc, metallic aluminium, magnesium metal and metallic iron as the metal sprinkled than work in copper；
Deionized water；
Sodium hydroxide solution, potassium hydroxide solution and lithium hydroxide solution as aqueous slkali；
Ammonium hydroxide；
Ethyl alcohol.
Then:
Embodiment 1
The specific steps of preparation are as follows:
Step 1, the ratio for being 0.8:1 according to the volume ratio of the silver nitrate solution of 20mmol/L and the liquor kalii iodide of 5mol/L
Silver nitrate solution is instilled in liquor kalii iodide and is vigorously stirred, obtains [AgI by example2]-Complex solution.
Step 2, according to the potassium iodide of the copper nitrate solution of 0.1mol/L, the sodium sulfite solution of 0.7mol/L and 3mol/L
The volume ratio of solution is the ratio of 0.3:0.7:1, instills in liquor kalii iodide and is vigorously stirred after the above two are mixed, obtains
[CuI2]-Complex solution.
Step 3, according to [AgI2]-Complex solution and [CuI2]-Complex solution volume ratio be 0.8:1 ratio, will
The two mixing, obtains complex compound mixed solution.
It step 4, be to electrode, conductive substrates or conductive template as reference electrode, graphite flake using silver-silver chloride is work electricity
Pole is placed in together in complex compound mixed solution, the electro-deposition 45min under working electrode is relative to the voltage of reference electrode -0.5V；
Wherein, conductive substrates are indium tin oxide-coated glass, and conductive template is the alumina formwork with conductive film, and it is mixed to be placed in complex compound
The spacing for closing reference electrode and working electrode in solution is 0.2cm, is 8cm to the spacing of electrode and working electrode, in conduction
Yellow gold is obtained in substrate surface or conductive template.
Step 5, the yellow gold on conductive substrates surface is immersed in saturated solution of potassium iodide after cleaning, uses deionized water
It is cleaned, obtains pure yellow gold in conductive substrates surface；Or the conductive template for being equipped with yellow gold is immersed
After being cleaned in saturated solution of potassium iodide, first it is cleaned using deionized water, reuses conductive tape for conductive template
Conductive film is placed in aqueous slkali with the metal bonding sprinkled than work in copper and erodes template, later, removes conductive tape and compares work in copper
Bold and vigorous metal, wherein the conductive film of conductive template with a thickness of 150nm, the metal sprinkled than work in copper is metallic zinc, and aqueous slkali is hydrogen
Sodium hydroxide solution, in obtaining pure yellow gold on conductive film.
Step 6, by pure yellow gold on conductive substrates surface pure yellow gold or conductive film immerse according to
In the mixed solution that the ratio that the ammonium hydroxide of 25wt% and the volume ratio of ethyl alcohol are 1.5:1 is prepared, and it is passed through oxygen thereto
40min is made bore dia≤20nm nanoporous Ag films of nano-porous silver or is similar to shown in Fig. 1 d, and such as Fig. 1 e
In curve shown in nano-porous silver bore dia≤20nm nanoporous silver nanowires.
Embodiment 2
The specific steps of preparation are as follows:
It step 1, is 0.98:1 according to the volume ratio of the silver nitrate solution of 25mmol/L and the liquor kalii iodide of 4.5mol/L
Ratio, by silver nitrate solution instill liquor kalii iodide in and be vigorously stirred, obtain [AgI2]-Complex solution.
Step 2, according to the copper nitrate solution of 0.15mol/L, the iodine of the sodium sulfite solution of 0.65mol/L and 3.8mol/L
The volume ratio for changing potassium solution is the ratio of 0.35:0.65:1, instills in liquor kalii iodide and is vigorously stirred after the above two are mixed,
Obtain [CuI2]-Complex solution.
Step 3, according to [AgI2]-Complex solution and [CuI2]-Complex solution volume ratio be 0.98:1 ratio,
The two is mixed, complex compound mixed solution is obtained.
It step 4, be to electrode, conductive substrates or conductive template as reference electrode, graphite flake using silver-silver chloride is work electricity
Pole is placed in together in complex compound mixed solution, the electro-deposition under working electrode is relative to the voltage of reference electrode -0.55V
35min；Wherein, conductive substrates are indium tin oxide-coated glass, and conductive template is the alumina formwork with conductive film, are placed in network
The spacing for closing reference electrode and working electrode in object mixed solution is 0.7cm, is to the spacing of electrode and working electrode
6.5cm obtains yellow gold in conductive substrates surface or conductive template.
Step 5, the yellow gold on conductive substrates surface is immersed in saturated solution of potassium iodide after cleaning, uses deionized water
It is cleaned, obtains pure yellow gold in conductive substrates surface；Or the conductive template for being equipped with yellow gold is immersed
After being cleaned in saturated solution of potassium iodide, first it is cleaned using deionized water, reuses conductive tape for conductive template
Conductive film is placed in aqueous slkali with the metal bonding sprinkled than work in copper and erodes template, later, removes conductive tape and compares work in copper
Bold and vigorous metal, wherein the conductive film of conductive template with a thickness of 180nm, the metal sprinkled than work in copper is metallic zinc, and aqueous slkali is hydrogen
Sodium hydroxide solution, in obtaining pure yellow gold on conductive film.
Step 6, by pure yellow gold on conductive substrates surface pure yellow gold or conductive film immerse according to
In the mixed solution that the ratio that the ammonium hydroxide of 25.8wt% and the volume ratio of ethyl alcohol are 1.33:1 is prepared, and it is passed through oxygen thereto
45min is made bore dia≤20nm nanoporous Ag films of nano-porous silver or is similar to shown in Fig. 1 d, and such as Fig. 1 e
In curve shown in nano-porous silver bore dia≤20nm nanoporous silver nanowires.
Embodiment 3
The specific steps of preparation are as follows:
It step 1, is 1.16:1's according to the volume ratio of the silver nitrate solution of 30mmol/L and the liquor kalii iodide of 4mol/L
Silver nitrate solution is instilled in liquor kalii iodide and is vigorously stirred, obtains [AgI by ratio2]-Complex solution.
Step 2, according to the iodate of the copper nitrate solution of 0.2mol/L, the sodium sulfite solution of 0.6mol/L and 4.5mol/L
The volume ratio of potassium solution is the ratio of 0.4:0.6:1, instills in liquor kalii iodide and is vigorously stirred after the above two are mixed, obtains
[CuI2]-Complex solution.
Step 3, according to [AgI2]-Complex solution and [CuI2]-Complex solution volume ratio be 1.16:1 ratio,
The two is mixed, complex compound mixed solution is obtained.
It step 4, be to electrode, conductive substrates or conductive template as reference electrode, graphite flake using silver-silver chloride is work electricity
Pole is placed in together in complex compound mixed solution, the electro-deposition 25min under working electrode is relative to the voltage of reference electrode -0.6V；
Wherein, conductive substrates are indium tin oxide-coated glass, and conductive template is the alumina formwork with conductive film, and it is mixed to be placed in complex compound
The spacing for closing reference electrode and working electrode in solution is 1.1cm, is 5cm to the spacing of electrode and working electrode, in conduction
Yellow gold is obtained in substrate surface or conductive template.
Step 5, the yellow gold on conductive substrates surface is immersed in saturated solution of potassium iodide after cleaning, uses deionized water
It is cleaned, obtains pure yellow gold in conductive substrates surface；Or the conductive template for being equipped with yellow gold is immersed
After being cleaned in saturated solution of potassium iodide, first it is cleaned using deionized water, reuses conductive tape for conductive template
Conductive film is placed in aqueous slkali with the metal bonding sprinkled than work in copper and erodes template, later, removes conductive tape and compares work in copper
Bold and vigorous metal, wherein the conductive film of conductive template with a thickness of 200nm, the metal sprinkled than work in copper is metallic zinc, and aqueous slkali is hydrogen
Sodium hydroxide solution, in obtaining pure yellow gold on conductive film.
Step 6, by pure yellow gold on conductive substrates surface pure yellow gold or conductive film immerse according to
In the mixed solution that the ratio that the ammonium hydroxide of 26.5wt% and the volume ratio of ethyl alcohol are 1.16:1 is prepared, and it is passed through oxygen thereto
Bore dia≤20nm nanoporous Ag films or as shown in Figure 1 d of nano-porous silver are made in 50min, and as in Fig. 1 e
Bore dia≤20nm nanoporous silver nanowires of nano-porous silver shown in curve.
Embodiment 4
The specific steps of preparation are as follows:
It step 1, is 1.33:1 according to the volume ratio of the silver nitrate solution of 35mmol/L and the liquor kalii iodide of 3.5mol/L
Ratio, by silver nitrate solution instill liquor kalii iodide in and be vigorously stirred, obtain [AgI2]-Complex solution.
Step 2, according to the copper nitrate solution of 0.25mol/L, the iodine of the sodium sulfite solution of 0.55mol/L and 5.3mol/L
The volume ratio for changing potassium solution is the ratio of 0.45:0.55:1, instills in liquor kalii iodide and is vigorously stirred after the above two are mixed,
Obtain [CuI2]-Complex solution.
Step 3, according to [AgI2]-Complex solution and [CuI2]-Complex solution volume ratio be 1.33:1 ratio,
The two is mixed, complex compound mixed solution is obtained.
It step 4, be to electrode, conductive substrates or conductive template as reference electrode, graphite flake using silver-silver chloride is work electricity
Pole is placed in together in complex compound mixed solution, the electro-deposition under working electrode is relative to the voltage of reference electrode -0.65V
15min；Wherein, conductive substrates are indium tin oxide-coated glass, and conductive template is the alumina formwork with conductive film, are placed in network
The spacing for closing reference electrode and working electrode in object mixed solution is 1.5cm, is to the spacing of electrode and working electrode
3.5cm obtains yellow gold in conductive substrates surface or conductive template.
Step 5, the yellow gold on conductive substrates surface is immersed in saturated solution of potassium iodide after cleaning, uses deionized water
It is cleaned, obtains pure yellow gold in conductive substrates surface；Or the conductive template for being equipped with yellow gold is immersed
After being cleaned in saturated solution of potassium iodide, first it is cleaned using deionized water, reuses conductive tape for conductive template
Conductive film is placed in aqueous slkali with the metal bonding sprinkled than work in copper and erodes template, later, removes conductive tape and compares work in copper
Bold and vigorous metal, wherein the conductive film of conductive template with a thickness of 230nm, the metal sprinkled than work in copper is metallic zinc, and aqueous slkali is hydrogen
Sodium hydroxide solution, in obtaining pure yellow gold on conductive film.
Step 6, by pure yellow gold on conductive substrates surface pure yellow gold or conductive film immerse according to
In the mixed solution that the ratio that the ammonium hydroxide of 27.3wt% and the volume ratio of ethyl alcohol are 0.98:1 is prepared, and it is passed through oxygen thereto
55min is made bore dia≤20nm nanoporous Ag films of nano-porous silver or is similar to shown in Fig. 1 d, and such as Fig. 1 e
In curve shown in nano-porous silver bore dia≤20nm nanoporous silver nanowires.
Embodiment 5
The specific steps of preparation are as follows:
Step 1, the ratio for being 1.5:1 according to the volume ratio of the silver nitrate solution of 40mmol/L and the liquor kalii iodide of 3mol/L
Silver nitrate solution is instilled in liquor kalii iodide and is vigorously stirred, obtains [AgI by example2]-Complex solution.
Step 2, according to the potassium iodide of the copper nitrate solution of 0.3mol/L, the sodium sulfite solution of 0.5mol/L and 6mol/L
The volume ratio of solution is the ratio of 0.5:0.5:1, instills in liquor kalii iodide and is vigorously stirred after the above two are mixed, obtains
[CuI2]-Complex solution.
Step 3, according to [AgI2]-Complex solution and [CuI2]-Complex solution volume ratio be 1.5:1 ratio, will
The two mixing, obtains complex compound mixed solution.
It step 4, be to electrode, conductive substrates or conductive template as reference electrode, graphite flake using silver-silver chloride is work electricity
Pole is placed in together in complex compound mixed solution, the electro-deposition 5min under working electrode is relative to the voltage of reference electrode -0.7V；
Wherein, conductive substrates are indium tin oxide-coated glass, and conductive template is the alumina formwork with conductive film, and it is mixed to be placed in complex compound
The spacing for closing reference electrode and working electrode in solution is 2cm, is 2cm to the spacing of electrode and working electrode, in conductive liner
Yellow gold is obtained in bottom surface or conductive template.
Step 5, the yellow gold on conductive substrates surface is immersed in saturated solution of potassium iodide after cleaning, uses deionized water
It is cleaned, obtains pure yellow gold in conductive substrates surface；Or the conductive template for being equipped with yellow gold is immersed
After being cleaned in saturated solution of potassium iodide, first it is cleaned using deionized water, reuses conductive tape for conductive template
Conductive film is placed in aqueous slkali with the metal bonding sprinkled than work in copper and erodes template, later, removes conductive tape and compares work in copper
Bold and vigorous metal, wherein the conductive film of conductive template with a thickness of 250nm, the metal sprinkled than work in copper is metallic zinc, and aqueous slkali is hydrogen
Sodium hydroxide solution, in obtaining pure yellow gold on conductive film.
Step 6, by pure yellow gold on conductive substrates surface pure yellow gold or conductive film immerse according to
In the mixed solution that the ratio that the ammonium hydroxide of 28wt% and the volume ratio of ethyl alcohol are 0.8:1 is prepared, and it is passed through oxygen thereto
60min is made bore dia≤20nm nanoporous Ag films of nano-porous silver or is similar to shown in Fig. 1 d, and such as Fig. 1 e
In curve shown in nano-porous silver bore dia≤20nm nanoporous silver nanowires.
It selects the indium tin oxide-coated glass or fluorine-doped tin oxide electro-conductive glass or silicon wafer as conductive substrates respectively again, makees
For the alumina formwork with conductive film of conductive template or the polystyrene sphere template with conductive film or using photoetching or
The template that the method for electron beam lithography is obtained in the surface of indium tin oxide-coated glass or fluorine-doped tin oxide electro-conductive glass or silicon wafer,
As the metallic zinc or metallic aluminium or magnesium metal or metallic iron of the metal sprinkled than work in copper, as aqueous slkali sodium hydroxide solution or
Potassium hydroxide solution or lithium hydroxide solution, repeat above-described embodiment 1-5, be equally made as or be similar to Fig. 1 d, Fig. 2 b and
Shown in Fig. 3 b, and bore dia≤20nm nanoporous Ag films of the nano-porous silver as shown in the curve in Fig. 1 e, or
Nanoporous silver nanowires or nano-porous silver nanometer stick array or nanoporous silver micron ball array.
Obviously, those skilled in the art can carry out the method for the porous silver of electrodeposited nanocrystalline of the invention various
Modification and variation is without departing from the spirit and scope of the present invention.If in this way, belonging to this to these modifications and changes of the present invention
Within the scope of invention claim and its equivalent technologies, then the present invention is also intended to include these modifications and variations.
Claims (8)
1. a kind of method of the porous silver of electrodeposited nanocrystalline is made of, it is characterised in that complete electrodeposition process and removal alloyage
At steps are as follows:
Step 1, it is 0.8-1.5 according to the volume ratio of the silver nitrate solution of 20-40mmol/L and the liquor kalii iodide of 3-5mol/L:
Silver nitrate solution is instilled in liquor kalii iodide and is vigorously stirred, obtains [AgI by 1 ratio2]-Complex solution；
Step 2, according to the copper nitrate solution of 0.1-0.3mol/L, the sodium sulfite solution of 0.5-0.7mol/L and 3-6mol/L
The volume ratio of liquor kalii iodide is the ratio of 0.3-0.5:0.5-0.7:1, is instilled in liquor kalii iodide simultaneously after the above two are mixed
It is vigorously stirred, obtains [CuI2]-Complex solution；
Step 3, according to [AgI2]-Complex solution and [CuI2]-Complex solution volume ratio be 0.8-1.5:1 ratio, will
The two mixing, obtains complex compound mixed solution；
It step 4, is to electrode, conductive substrates or conductive template for working electrode by reference electrode, graphite flake of silver-silver chloride,
It is placed in complex compound mixed solution together, electro-deposition is extremely under working electrode is relative to the voltage of reference electrode-(0.5-0.7) V
Few 5min obtains yellow gold in conductive substrates surface or conductive template；
Step 5, the yellow gold on conductive substrates surface is immersed in saturated solution of potassium iodide and is cleaned, obtained in conductive substrates surface
Pure yellow gold, or will be equipped in the conductive template immersion saturated solution of potassium iodide of yellow gold after cleaning, use conduction
The conductive film of conductive template is placed in aqueous slkali with the metal bonding sprinkled than work in copper and erodes template by adhesive tape, later, removal
Conductive tape and the metal sprinkled than work in copper, in obtaining pure yellow gold on conductive film；
Step 6, yellow gold pure on conductive substrates surface pure yellow gold or conductive film is immersed according to 25-
In the mixed solution that the ratio that the ammonium hydroxide of 28wt% and the volume ratio of ethyl alcohol are 0.8-1.5:1 is prepared, and it is passed through oxygen thereto
Bore dia≤20nm nanoporous the Ag films or nanoporous silver nanowires of nano-porous silver are made at least 40min, or
Nano-porous silver nanometer stick array or nanoporous silver micron ball array.
2. the method for the porous silver of electrodeposited nanocrystalline according to claim 1, it is characterized in that conductive substrates are indium oxide
Tin electro-conductive glass or fluorine-doped tin oxide electro-conductive glass or silicon wafer.
3. the method for the porous silver of electrodeposited nanocrystalline according to claim 1, it is characterized in that conductive template is with leading
The alumina formwork of electrolemma, or the polystyrene sphere template with conductive film, or use photoetching or the method for electron beam lithography
In the template that the surface of indium tin oxide-coated glass or fluorine-doped tin oxide electro-conductive glass or silicon wafer obtains.
4. the method for the porous silver of electrodeposited nanocrystalline according to claim 1, it is characterized in that it is molten to be placed in complex compound mixing
The spacing of reference electrode and working electrode in liquid is 0.2-2cm, is 2-8cm to the spacing of electrode and working electrode.
5. the method for the porous silver of electrodeposited nanocrystalline according to claim 1, it is characterized in that the conductive film of conductive template
Thickness >=150nm.
6. the method for the porous silver of electrodeposited nanocrystalline according to claim 1, it is characterized in that being than the metal that work in copper sprinkle
Metallic zinc or metallic aluminium or magnesium metal or metallic iron.
7. the method for the porous silver of electrodeposited nanocrystalline according to claim 1, it is characterized in that by conductive substrates surface
Yellow gold or be equipped with yellow gold conductive template immerse saturated solution of potassium iodide in clean after, using deionized water to its into
Row cleaning.
8. the method for the porous silver of electrodeposited nanocrystalline according to claim 1, it is characterized in that aqueous slkali is sodium hydroxide
Solution or potassium hydroxide solution or lithium hydroxide solution.
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| CN111326754B (en) * | 2020-03-10 | 2021-05-14 | 中南林业科技大学 | Preparation method of fusiform platinum nanoparticles |
| CN113968602A (en) * | 2021-10-25 | 2022-01-25 | 中国科学院合肥物质科学研究院 | Method for removing nitrified nitrogen in water through electro-catalysis |
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