CN101597775A - A kind of nanoporous gold electrochemical preparation method - Google Patents
A kind of nanoporous gold electrochemical preparation method Download PDFInfo
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- CN101597775A CN101597775A CNA2009100166557A CN200910016655A CN101597775A CN 101597775 A CN101597775 A CN 101597775A CN A2009100166557 A CNA2009100166557 A CN A2009100166557A CN 200910016655 A CN200910016655 A CN 200910016655A CN 101597775 A CN101597775 A CN 101597775A
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Abstract
The present invention relates to a kind of nanoporous gold electrochemical preparation method, may further comprise the steps: (1) is heated to molten state with pure metallic aluminum, gold, fully mixes, and is frozen into Al-Au presoma alloy then under certain speed of cooling; (2) the presoma alloy of above-mentioned preparation is carried out electrochemistry in neutral electrolyte solution and take off Alloying Treatment; (3) nano-porous gold after will handling cleans in distilled water to neutral, dries then, promptly makes nano-porous gold.The invention has the beneficial effects as follows: the cost that greatly reduces the preparation nano-porous gold; The electrolyte solution that adopts is neutral sodium-chlor or Klorvess Liquid, and nontoxic nonirritant is pollution-free, environmental friendliness; And can the structure and the size of nano-porous gold be regulated and control according to composition, operating voltage and the working temperature of presoma alloy.
Description
Technical field
The present invention relates to a kind of nanoporous gold electrochemical preparation method, belong to the preparation of nanomaterials technical field.
Background technology
Nano porous metal is the material with nano-scale hole, its aperture size be several nanometers to the hundreds of nanometer, the hole of nano-scale and ligament are three-dimensional co-continuous and mutually connect.Nano porous metal is a kind of special porous material, nano level aperture size makes it have higher specific surface area and other unique physics, chemistry and mechanical property, for example, very high chemical catalysis activity, unique conductivity, higher Young's modulus and intensity etc.Therefore, nano porous metal has very big application potential in a lot of fields, and the applied research of carrying out at present mainly contains fuel cell, gas phase and liquid-phase catalysis, excites, sensing, surface enhanced Raman scattering, microfluidic control etc.
At present, taking off alloyage is to prepare the main method of cavernous structure nano porous metal at random, the object of choosing mostly is the binary solid solution alloy, by selecting suitable caustic solution, will be wherein comparatively active dissolving metal, remaining comparatively inert atoms metal is through the final nano-porous structure that forms co-continuous of diffusion reorganization.As far back as 1979, and A.J.Forty (Forty, A.J.Nature 1979,282, and 597.) utilize concentrated nitric acid that the Ag-Au alloy is taken off alloy treatment, prepared nano-porous gold.Calendar year 2001, people (Erlebacher J such as Jonah Erlebacher, Aziz M, KarmaA, et al.Nature, 2001,410 (22): 450-453.) Ag-32 at.%Au and Ag-24 at.%Au are taken off after the alloy, made thickness and be about the nanoporous gold thin film that 700nm, aperture size are about 10nm with concentrated nitric acid.2004, people (Ding Y, Kim Y, Erlebacher J.Advanced Materials, 2004,16 (21): 1897-1900.) use 70wt.%HNO such as Ding Yi
3Ag, Au massfraction be 50% the color leaf of commercial platinum and carried out taking off alloy treatment, made thickness and be about 100nm, aperture size is about the nanoporous gold thin film of 20nm.2005, people (Dursun A such as Dursun Aziz, Pugh D, Corcoran S.Journal of the Electrochemical Society, 2005,152 (2): B65-B72.) with electrolysis corrosive mode Ag-20at.%Au, Ag-25at.%Au and Ag-30at.%Au have been carried out taking off alloy, the electrolytic solution that adopts in the corrosion process is the HClO of 0.1mol/L
42005, the Jing-FangHuang in China Taiwan and I-Wen Sun (Huang Jing-Fang, Sun I.-Wen.Advanced Functional Materials, 2005,15:989-994.) at first in gold electrode surfaces with the zinc-plated formation of the mode of galvanic deposit Zn-Au alloy, subsequently at ZnCl
2Carry out electrolysis in the-EMIC solion and take off alloy treatment, made nano-porous gold.2008, people such as J.Snyder (J.Snyder, K.Livi, J.Erlebacher, J.Electrochem.Soc.155 (2008) C464.) carried out taking off Alloying Treatment to the Ag-Au alloy in silver nitrate solution, prepared nano-porous gold.2009, people such as Z.H.Zhang (Z.H.Zhang, Y.Wang, Z.Qi, J.K.Lin, X.F.Bian, J.Phys.Chem.C 113 (2009) 1308.) the Al-Au alloy is taken off the nano-porous gold that Alloying Treatment has prepared pore structure and size adjustable in hydrochloric acid or sodium hydroxide solution.
In above-mentioned preparation technology or method, adopt the Ag-Au alloy system to prepare nano-porous gold, remove precious metals ag by corrosion, its cost is than higher; And Zn-Au surface alloying/take off Alloying Treatment prepares the porous gold, its technology more complicated, and also the composition of Zn-Au alloy is difficult to accurately control; Adopt corrosive, that non-ambient is friendly acidity or basic solution more, contaminate environment, poisonous have a pungency, works under hard conditions.
Summary of the invention
The objective of the invention is to overcome above-mentioned the deficiencies in the prior art, provide a kind of low cost, technology is simple, nano-porous structure is controlled, the preparation method of nontoxic pollution-free, eco-friendly nano-porous gold.
The present invention is achieved by the following technical solutions:
Described nanoporous gold electrochemical preparation method may further comprise the steps:
(1) pure metallic aluminum, gold are heated to molten state, fully mix, under certain speed of cooling, be frozen into Al-Au presoma alloy then; In the described Al-Au presoma alloy, the shared atomic percent of Au is 10～60%, and all the other are Al, and the purity of Al and Au is＞99.0wt.%.
(2) the presoma alloy of above-mentioned preparation is carried out electrochemistry in neutral electrolyte solution and take off Alloying Treatment; The concrete steps of taking off Alloying Treatment are: with the Al-Au alloy is working electrode, and graphite is negative electrode, carries out electrochemistry and take off Alloying Treatment 0.1～48h under the working temperature of the operating voltage of 0.3-2.5V and-20～90 ℃.
(3) nano-porous gold after will handling cleans in distilled water to neutral, dries then, promptly makes nano-porous gold.For reaching better effect, the speed of cooling in the step (1) is 0.01-10
6K/s; Neutral electrolyte solution described in the step (2) is the sodium chloride solution of 0.01-26wt.% or the Klorvess Liquid of 0.01-25wt.%, is preferably the sodium-chlor of 10wt.% or the Klorvess Liquid of 10wt.%.
Method of the present invention is compared with existing nano-porous gold preparation technology, has the following advantages: (1) this method is selected the presoma alloy of Al-Au alloy as nano-porous gold for use, can reduce the cost of preparation nano-porous gold greatly.(2) electrolyte solution of this method employing is neutral sodium-chlor or Klorvess Liquid, and nontoxic nonirritant is pollution-free, environmental friendliness.(3) present method can be regulated and control the structure and the size of nano-porous gold according to composition, operating voltage and the working temperature of presoma alloy.
Embodiment
The invention will be further described below in conjunction with specific embodiment.
Embodiment 1
(1) according to atomic percent 33.4%Au, all the other are the proportioning of Al, the Al-Au alloy is put into smelting furnace be heated to molten state, make its alloying through fully stirring.With argon gas fused liquid is blown out under 0.1MPa pressure fast, Quench on the copper roller of high speed rotating, speed of cooling are 10
3-10
6K/s, obtaining thickness is the 20-40 micron, and width is the 2-5 millimeter, and length is 1-5 centimetre alloy thin band.
(2) under 25 ℃, be working electrode (anode) with the Al-Au alloy, graphite is negative electrode, and the 10wt.% sodium chloride solution is an ionogen, and operating voltage is 1.5V, carries out electrochemistry and takes off Alloying Treatment 0.5 hour.
(3) reacted product is collected, washed repeatedly to electrolyte solution clean fully (wide pH value test paper check flushing distilled water is neutral) with distilled water.Under 25 ℃, dry then and preserve.Aperture, hole wall size are about the 10-20 nanometer, and the pore structure uniform distribution.
Embodiment 2
(1) according to atomic percent 20%Au, all the other are the proportioning of Al, the Al-Au alloy is put into smelting furnace be heated to molten state, make its alloying through fully stirring.With argon gas fused liquid is blown out under 0.1MPa pressure fast, Quench on the copper roller of high speed rotating, speed of cooling are 10
3-10
5K/s, obtaining thickness is the 30-50 micron, and width is the 2-5 millimeter, and length is 5-20 centimetre alloy thin band.
(2) under 70 ℃, be working electrode (anode) with the Al-Au alloy, graphite is negative electrode, and the 10wt.% sodium chloride solution is an ionogen, and operating voltage is 2.0V, carries out electrochemistry and takes off Alloying Treatment 0.1 hour.
(3) reacted product is collected, washed repeatedly to electrolyte solution clean fully (wide pH value test paper check flushing distilled water is neutral) with distilled water.Under 25 ℃, dry then and preserve.This nano-porous gold has double mode pore distribution.
Embodiment 3
Other steps are identical with embodiment one, and argon gas is changed to nitrogen, and the 10wt.% sodium chloride solution is changed to the 10wt.% Klorvess Liquid.This nano-porous gold pore structure is evenly distributed, and aperture, hole wall size are about the 10-20 nanometer.
Embodiment 4
(1) according to atomic percent 33.4%Au, all the other are the proportioning of Al, and the Al-Au alloy is put into smelting furnace.Alloy is heated to molten state, makes its alloying through fully stirring.With argon gas fused liquid is blown out under 0.1MPa pressure fast, Quench on the copper roller of high speed rotating, speed of cooling are 10
3-10
6K/s, obtaining thickness is the 20-40 micron, and width is the 2-5 millimeter, and length is 1-5 centimetre alloy thin band.
(2) under-10 ℃, be working electrode (anode) with the Al-Au alloy, graphite is negative electrode, and the 10wt.% sodium chloride solution is an ionogen, and operating voltage is 1.5V, carries out electrochemistry and takes off Alloying Treatment 1.5 hours.
(3) reacted product is collected, washed repeatedly to electrolyte solution clean fully (wide pH value test paper check flushing distilled water is neutral) with distilled water.Under 25 ℃, dry then and preserve.Aperture, hole wall size are about the 10-15 nanometer, and the pore structure uniform distribution.
Embodiment 5
(1) according to atomic percent 40%Au, all the other are the proportioning of Al, and the Al-Au alloy is put into smelting furnace.Alloy is heated to molten state, makes its alloying through fully stirring.With argon gas fused liquid is blown out under 0.1MPa pressure fast, Quench on the copper roller of high speed rotating, speed of cooling are 10
3-10
6K/s, obtaining thickness is the 40-60 micron, and width is the 2-6 millimeter, and length is 2-5 centimetre alloy thin band.
(2) under 25 ℃, be working electrode (anode) with the Al-Au alloy, graphite is negative electrode, and the 10wt.% sodium chloride solution is an ionogen, and operating voltage is 0.8V, carries out electrochemistry and takes off Alloying Treatment 10 hours.
(3) reacted product is collected, washed repeatedly to chemical corrosion solution clean fully (wide pH value test paper check flushing distilled water is neutral) with distilled water.Under 25 ℃, dry then and preserve.This nano-porous gold is the nanoporous metal/composite material with two kinds of nano-porous structures, and the cellular structure mesopore is of a size of the 20-40 nanometer.
Embodiment 6
(1) according to atomic percent 33.4%Au, all the other are the proportioning of Al, and the Al-Au alloy is put into smelting furnace.Alloy is heated to molten state, makes its alloying through fully stirring.With argon gas fused liquid is blown out under 0.1MPa pressure fast, the fused liquid metal is solidified in the metal copper mold, speed of cooling is 10-100K/s, and preparing thickness is 1mm, wide for the alloy sheet of 5mm, length are 4cm, and perhaps diameter is that 1mm, length are the alloy bar of 6cm.
(2) under 25 ℃, be working electrode (anode) with the Al-Au alloy, graphite is negative electrode, and the 10wt.% sodium chloride solution is an ionogen, and operating voltage is 1.5V, carries out electrochemistry and takes off Alloying Treatment 24 hours.
(3) reacted product is collected, washed repeatedly to electrolyte solution clean fully (wide pH value test paper check flushing distilled water is neutral) with distilled water.Under 25 ℃, dry then and preserve.Aperture, hole wall size are about the 20-40 nanometer, and the pore structure uniform distribution.
Embodiment 7
Removing electrolyte solution is the sodium chloride solution of 26wt.%, and taking off the Alloying Treatment time is outside the 48h, and other are operated with embodiment 6.This nano-porous gold pore structure is evenly distributed, and aperture, hole wall size are about the 30-50 nanometer.
Embodiment 8
Remove according to atomic percent 60%Au, all the other carry out proportioning for Al, and electrolyte solution is the Klorvess Liquid of 0.01wt.%, and taking off the Alloying Treatment time is outside the 10h, and other are operated with embodiment 1.This nano-porous gold pore structure is evenly distributed, and aperture, hole wall size are about the 80-100 nanometer.
Claims (6)
1. nanoporous gold electrochemical preparation method is characterized in that may further comprise the steps:
(1) pure metallic aluminum, gold are heated to molten state, fully mix, under certain speed of cooling, be frozen into Al-Au presoma alloy then;
(2) the presoma alloy of above-mentioned preparation is carried out electrochemistry in neutral electrolyte solution and take off Alloying Treatment;
(3) nano-porous gold after will handling cleans in distilled water to neutral, dries then, promptly makes nano-porous gold.
2. the preparation method of nano-porous gold according to claim 1, it is characterized in that: in the described Al-Au presoma alloy, the shared atomic percent of Au is 10～60%, and all the other are Al.
3. the preparation method of nano-porous gold according to claim 1 and 2, it is characterized in that: the process of taking off Alloying Treatment described in the step (2) is: with the Al-Au alloy is working electrode, graphite is negative electrode, carries out electrochemistry and take off Alloying Treatment 0.1～48h under the working temperature of the operating voltage of 0.3-2.5V and-20～90 ℃.
4. the preparation method of nano-porous gold according to claim 1 and 2, it is characterized in that: the speed of cooling in the step (1) is 0.01-10
6K/s.
5. the preparation method of nano-porous gold according to claim 1 and 2, it is characterized in that: the neutral electrolyte solution described in the step (2) is the sodium chloride solution of 0.01-26wt.% or the Klorvess Liquid of 0.01-25wt.%.
6. the preparation method of nano-porous gold according to claim 5, it is characterized in that: the neutral electrolyte solution described in the step (2) is the sodium-chlor of 10wt.% or the Klorvess Liquid of 10wt.%.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102706937A (en) * | 2012-06-04 | 2012-10-03 | 中山大学 | Micro-nano porous bismuth electrode and preparation method thereof |
| CN104942281A (en) * | 2015-07-01 | 2015-09-30 | 清华大学 | Porous gold nanowire and manufacturing method and application thereof |
| CN105107499A (en) * | 2015-09-22 | 2015-12-02 | 西北有色金属研究院 | Preparation method of doped nanoporous gold (NPG) with small pore diameter and large specific surface area |
| CN106395739A (en) * | 2015-07-29 | 2017-02-15 | 上海师范大学 | Nano-grade porous tin dioxide film gas sensitive material, and preparation method and application thereof |
| CN106757174A (en) * | 2017-02-23 | 2017-05-31 | 黄芃 | A kind of electro-deposition prepares the method and device of metal dust |
| CN110146531A (en) * | 2019-05-22 | 2019-08-20 | 中山大学 | A kind of large scale co-continuous porous foam bismuth and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101337193B (en) * | 2008-08-04 | 2010-07-14 | 山东大学 | Method of surface nano-crystallization of noble metal catalyst |
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2009
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102706937A (en) * | 2012-06-04 | 2012-10-03 | 中山大学 | Micro-nano porous bismuth electrode and preparation method thereof |
| CN104942281A (en) * | 2015-07-01 | 2015-09-30 | 清华大学 | Porous gold nanowire and manufacturing method and application thereof |
| CN106395739A (en) * | 2015-07-29 | 2017-02-15 | 上海师范大学 | Nano-grade porous tin dioxide film gas sensitive material, and preparation method and application thereof |
| CN106395739B (en) * | 2015-07-29 | 2018-12-14 | 上海师范大学 | A kind of nanoporous tin dioxide thin film gas sensitive and its preparation method and application |
| CN105107499A (en) * | 2015-09-22 | 2015-12-02 | 西北有色金属研究院 | Preparation method of doped nanoporous gold (NPG) with small pore diameter and large specific surface area |
| CN106757174A (en) * | 2017-02-23 | 2017-05-31 | 黄芃 | A kind of electro-deposition prepares the method and device of metal dust |
| CN110146531A (en) * | 2019-05-22 | 2019-08-20 | 中山大学 | A kind of large scale co-continuous porous foam bismuth and preparation method thereof |
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