CN101332438B - Method for coating noble metal on nano porous gold and prepared catalyst - Google Patents
Method for coating noble metal on nano porous gold and prepared catalyst Download PDFInfo
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- CN101332438B CN101332438B CN2008101388396A CN200810138839A CN101332438B CN 101332438 B CN101332438 B CN 101332438B CN 2008101388396 A CN2008101388396 A CN 2008101388396A CN 200810138839 A CN200810138839 A CN 200810138839A CN 101332438 B CN101332438 B CN 101332438B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/30—Hydrogen technology
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Abstract
The invention discloses a method for finishing a noble metal coating of a porous gold and the method comprises the following steps: the nanoporous gold is made by corroding gold-silver alloy; the nanoporous gold is soaked into a certain concentration of a solution containing chloroplatinic acid radical ions (or chloroplatinous acid radical ions, or chloropalladic acid radical ions, or chloropalladic acid radical ions, or the mixture) for an appropriate time to cause the surface of the nanoporous gold to absorb some noble metal ions, the other noble metal ions except for the noble metal ions absorbed on the surface of the nanoporous gold are washed clean, and the noble metal ions absorbed are reduced to a noble metal simple substance under proper electrochemical conditions, and the noble metal simple substance is tightly bonded on the pore wall of the nanoporous gold. The method of the invention can be used for preparing a catalyst which combines porous metals with ultra-low content of noble metals and can be applied in the catalytic fields of fuel cells and the like.
Description
Technical field
The present invention relates to a kind of reaction such as the oxidation of oxidization of methanol, hydrogen, the reduction of oxygen, the selective oxidation of CO that can be used for, ultralow noble metal carrying capacity, nano porous metal combination catalyst and preparation method relate in particular to that a kind of utilization is carried out coating noble metal to nano-porous gold and the ultralow noble metal carrying capacity nano porous metal combination catalyst for preparing.
Technical background
Fuel cell more and more is subjected to the attention of national governments, enterprise and scientific research institution owing to have higher energy conversion efficiency and lower pollution.Wherein Proton Exchange Membrane Fuel Cells is again because advantages such as its special started quickly at low temperature, compact conformation are highly suitable for the power supply as automobile and other removable facility.At present, hindering the business-like reason of fuel cell mainly is that it costs an arm and a leg, and the use amount of noble metal catalyst is too greatly the expensive one of the main reasons of fuel cell in the fuel cell.In order to promote the commercialization of fuel cell, obtain good economic benefit and social benefit, press for the carrying capacity that reduces noble metal catalyst in the fuel cell.
In order to improve the service efficiency of noble metal, traditional fuel-cell catalyst is Pt nanoparticle to be loaded on the carriers such as carbon dust.Because the Pt nanoparticle particle diameter limits, the service efficiency of catalyst is lower, in addition the resistance to corrosion of carbon dust etc. a little less than, catalyst in use loses activity easily, and this method for preparing catalyst complexity, homogeneity is poor.
Recently, the method for utilizing etch to prepare the nano porous metal material more and more is subject to people's attention.The alloy that composition and ratio is suitable can prepare high-specific surface area, inertia porous metals that even structure is adjustable by chemistry or electrochemical method corrosion.This nano structural material can be used as the particularly carrier of eelctro-catalyst of catalyst owing to have three-dimensional continuous duct and hole wall, higher specific surface area, good electrical conductivity and stronger excellent specific properties such as resistance to corrosion.Nineteen ninety Karl Sieradzki and Roger C.Newman have reported and can prepare porous gold structure (Karl sieradzki by the electrochemical corrosion electrum, Roger C.Newman " Micro-and Nano-porous MetallicStructures " US Patent, 4,977,038, Dec.11,1990).The applicant had obtained by corroding United States Patent (USP) and the international monopoly (JonahErlebacher that commercial electrum paper tinsel prepares high specific surface area porous gold thin film in 2004, Yi Ding " Method of Forming Nanoporous Membranes " US Patent, 6,805,972, Oct.19,2004; Worldwide Patent, WO 2004/020064, March 11,2004).The same year, the applicant has obtained based on the international monopoly of the metal film coating method of above porous gold thin film (Jonah Erlebacher, Yi Ding " Method of Plating Metal Leafs and Metal Membranes " Worldwide Patent, WO 2004/021481, Nov.3,2004).In the method for this porous metals plated film, the porous gold thin film is placed in and contains metal ion solution and contain on the gas interface of reducing agent, the gas-liquid phase reaction occurs in the duct of porous gold, thereby the hole wall surface of porous gold can plate layer of metal, the noble metal that particularly has catalytic activity uniformly.But this method only is fit to float over the very thin porous gold thin film on aqueous solution surface, and the amount of noble metal loading is bigger.
By retrieval, thus adopt surface ion absorption to add electrochemical reducing and the porous gold is carried out electrochemistry modify the method for preparing ultralow noble metal carrying capacity catalyst and do not appear in the newspapers.
Summary of the invention
At the deficiencies in the prior art, the purpose of this invention is to provide and a kind of the porous gold is carried out the new method of coating noble metal, particularly provide a kind of can be used for catalytic fields such as fuel cell, ultralow (atomic level) noble metal carrying capacity nano porous metal combination catalyst and preparation method.
Technical scheme of the present invention is to prepare nano-porous gold by the acid gilding silver alloy, nano-porous gold is placed certain density chloroplatinic acid radical ion (or the chloroplatinous acid radical ion that contains, or chlorine palladium acid ion, or the inferior palladium acid ion of chlorine, or the mixing between them) appropriate time in the solution, make its some precious metal ions of surface absorption, to rinse well except other precious metal ion the precious metal ion of porous gold surface absorption then, and under the suitable electrochemical conditions precious metal ion that adsorbs be reduced into precious metal simple substance and it is combined on the porous gold hole wall securely again.Number of times by the control soaking and reducing can be controlled the carrying capacity and the structure of modifying the noble metal on the porous gold.
Of the present invention nano-porous gold is carried out the method for coating noble metal, forms by following step:
(1) with thickness is 0.05-1000 μ m, width is 0.1-100cm, length is 0.1-1000cm, it is the nitric acid of 0.1～70wt.% that the electrum that golden amount ratio is 10-40% places concentration, under 0～50 ℃ of temperature, corrosion 1s～1000min with the nitric acid in clean alloy surface of deionized water and the hole, gets nano-porous gold then;
(2) nano-porous gold is fixed on the electrode, placing concentration is l μ mol dm
-3～10mol dm
-3The solution that contains precious metal ion in, soak 1s～10h, allow nano-porous gold metal surface absorption precious metal ion;
(3) nano-porous gold that the surface is adsorbed precious metal ion places the not solution or the deionized water of metal ion, soaking and washing 1min-10h, the non-metallic ion solution or the deionized water that more renew soak 1min-10h again, repeat 2-10 time, clean until the nano-porous gold surface clean;
(4) nano porous metal that clean surface has been adsorbed precious metal ion places electrolyte solution, apply one and make the fixed potential of precious metal ion reduction or carry out the linear scan of current potential to the current potential that can make the precious metal ion reduction, make precious metal ion be reduced into precious metal simple substance and also be combined in securely on the nano-porous gold hole wall from OCP;
(5) calculate the amount that is modified at the noble metal on the nano-porous gold hole wall by the electric weight of precious metal ion reduction peak and the valence state of precious metal ion; Then by repeating the number of times of (1)～(4) step, the carrying capacity and the structure of the noble metal of control decorated nanometer porous gold surface.
In the above-mentioned method of nano-porous gold being carried out coating noble metal:
The described electrum of step (1) is the preferred 0.1-50 μ of thickness m, the preferred 0.5-10cm of width, and the preferred 0.5-20cm of length, golden amount ratio is 37.5% commercial electrum paper tinsel.
The preferred 65-68wt.% of concentration of the described nitric acid of step (1); Preferred 20～30 ℃ of described corrosion temperature; The preferred 30min of described etching time.
The solution of the described precious metal ion of step (2) is the solution that contains the inferior palladium acid ion of chloroplatinic acid radical ion, chloroplatinous acid radical ion, chlorine palladium acid ion or chlorine, or the mixed solution of arbitrary volume ratio between them, the concentration of described precious metal ion solution is 1mmol dm preferably
-3, described soak time is 10min preferably.
The described cleaning solution of step (3) is deionized water preferably, and scavenging period is 10min preferably, cleans number of repetition preferably 3 times.
The described electrolyte solution of step (4) is HClO preferably
4Described method of reducing preferably applies the current potential linear scan from OCP to relative standard's hydrogen electrode 0V.
Preferred 2-5 time of the described number of repetition of step (5).
Utilize the catalyst of the method for the invention preparation, it is characterized in that described catalyst is that thickness is that 0.05-1000 μ m, width are that 0.1-100cm, length are evenly to be covered with the alloy sheet of subatomic layer to the precious metal simple substance of several atomic layer level thickness on the hole wall of 0.1-1000cm, surface and loose structure; Wherein said alloy sheet pattern is the nano-porous structure of three-dimensional perforate, and aperture size or pore wall thickness are 2～500nm.
Further preferably, described catalyst is that thickness is 0.1-50 μ m, and width is 0.5-10cm, and length is 0.5-20cm, evenly is covered with the alloy sheet of subatomic layer to the precious metal simple substance of several atomic layer level thickness on the hole wall of surface and loose structure; Wherein said alloy sheet pattern is the nano-porous structure of three-dimensional perforate, and aperture size or pore wall thickness are 2～100nm.
In the above-mentioned catalyst, the preferred Pt of described precious metal simple substance.
Method of the present invention is compared with the method that existing nano-porous gold surface metal plating layer is modified, and have the following advantages: (1) this kind method is not only applicable to the porous gold thin film to very thin thickness, is applicable to that also the very thick porous gold of thickness is carried out overlay coating to be modified.(2) this kind method applicable scope is wide, in principle, all can be modified on the nano-porous gold substrate as long as can form the stable metal ion that adsorbs in the nanoporous gold surface.(3) this method can realize the modification of subatomic layer to several atomic layer coating, is particularly suitable for noble metal catalyst is modified at ultralow carrying capacity on the substrate of nano-porous gold, realizes the high usage of noble metal catalyst.
Use the porous metals combination catalyst of method preparation of the present invention, carrying the type nanoparticle catalyst with traditional carbon compares, have the following advantages: (1) nano-porous gold has than the better electronic transmission performance of conventional fuel cell catalyst carrier (such as carbon dust), the ability of higher chemically-resistant electrochemical corrosion, in addition, because its three-dimensional open-celled structure can make the easier arrival electrode surface of reactant, is better catalyst carrier.(2) adsorb the method that adds electrochemical reduction by surface ion, can make noble metal catalyst arrive the structural modification of several atomic layers in the nanoporous gold surface with subatomic layer, thereby make noble metal catalyst almost absolutely play catalytic action, can keep 1-3 the order of magnitude of carrying capacity reduction that makes noble metal catalyst under the prerequisite of catalyst activity.
Description of drawings
The present invention will be further described below in conjunction with accompanying drawing.
Fig. 1 is SEM (SEM) photo of nanoporous gold thin film.
Be that thickness is 100nm, golden amount ratio is 37.5% commercial electrum paper tinsel, in the 68wt.% red fuming nitric acid (RFNA), and SEM (SEM) photo of the nanoporous gold thin film of room temperature (28 ℃) corrosion 30min preparation.Photo shows that the nano-porous gold of this method preparation has three-dimensional open-celled structure, and aperture size and pore wall thickness are more even, all about 20nm.
Fig. 2 is a cyclic voltammetry curve.
Be that nano-porous gold is at 0.5mmol dm
-3Platinum acid chloride solution soaked 30 seconds, with washed with de-ionized water three times, each 5min, then under three-electrode system, with the reversible hydrogen is reference, the cyclic voltammetry curve that the chloroplatinic acid radical ion that adsorbs by current potential linear scan reduced nano porous gold surface obtains, and the result shows, the nanoporous gold surface has been adsorbed the chloroplatinic acid radical ion really, and the electric weight by the integration reduction peak can calculate the quality of once modifying Pt.
Fig. 3 is a cyclic voltammetry curve.
Be that nano-porous gold is at 0.5mmol dm
-3Soaked 30 seconds in the platinum acid chloride solution, with washed with de-ionized water three times, each 5min, then under three-electrode system, with the reversible hydrogen is reference, by the chloroplatinic acid radical ion of current potential linear scan reduction porous gold surface absorption, same step is modified the Pt catalyst of the nano-porous gold load that obtains for 5 times at 0.1mol dm
-3HClO
4In, be the cyclic voltammetry curve of reference with the reversible hydrogen, the result shows that nano-porous gold is not covered fully by Pt simultaneously through on 5 modification porous gold Pt being arranged.
Fig. 4 is a cyclic voltammetry curve.
Be that nano-porous gold is at 0.5mmol dm
-3Soaked 30 seconds in the platinum acid chloride solution, with washed with de-ionized water three times, each 5min, then under three-electrode system, with the reversible hydrogen is reference, by the chloroplatinic acid radical ion of current potential linear scan reduced nano porous gold surface absorption, same step is modified the Pt catalyst of the porous gold load that obtains for 5 times at 0.1mol dm
-3HClO
4With 1mol dm
-3CH
3Among the OH, be the cyclic voltammetry curve of reference with the reversible hydrogen, the result normalizes on the Pt of unit mass, and the result shows the combination catalyst of this kind method preparation order of magnitude of quality current density raising than commercial Pt catalyst.
The specific embodiment:
Embodiment 1:
With the golden amount ratio of long 2cm, wide 1.8cm, thick 100nm is 37.5% commercial electrum paper tinsel, transfers in the 68wt.% red fuming nitric acid (RFNA), and room temperature (28 ℃) corrosion 30min prepares the nanoporous gold thin film, and its SEM photo as shown in Figure 1.
The nanoporous gold thin film for preparing is fixed on glass carbon (GC) electrode, at 0.5mmol dm
-3Soaked 30 seconds in the platinum acid chloride solution, adsorb some chloroplatinic acid radical ions in the nanoporous gold surface.
The nanoporous gold electrode that has adsorbed the chloroplatinic acid radical ion is spent ionized water clean three times, each 5min under three-electrode system, is a reference with the reversible hydrogen then, is adsorbed on the chloroplatinic acid radical ion of nanoporous gold surface by current potential linear scan reduction.The reduction electric weight of chloroplatinic acid radical ion can calculate the amount of the platinum of modifying by this electric weight as shown in Figure 2.
Repeat above step 5 and time prepare the nano-porous gold combination catalyst that platinum is modified.Its cyclic voltammetry curve as shown in Figure 3, the result shows to modify on the porous gold through 5 times Pt, the porous gold is not covered fully by Pt simultaneously.
Embodiment 2:
With the golden amount ratio of long 2cm, wide 1cm, thick 25 μ m is that 50% commercial electrum is transferred in the 68wt.% red fuming nitric acid (RFNA), and room temperature (28 ℃) corrosion 1h prepares thick nano-porous gold.
With the nano-porous gold for preparing at 1mmol dm
-3Soak 10min in the chloroplatinous acid solution, adsorb some chloroplatinous acid radical ions in the porous gold surface.
The nanoporous gold electrode that has adsorbed the chloroplatinous acid radical ion is spent ionized water to be cleaned three times, each 30min, then under three-electrode system, with the reversible hydrogen is reference, be adsorbed on the chloroplatinous acid radical ion of nanoporous gold surface by current potential linear scan reduction, prepare the nano-porous gold combination catalyst that platinum is modified.
Embodiment 3:
(1) be 20 μ m with thickness, width is 3cm, and length is 10cm, golden amount ratio be 37% electrum to place concentration be the nitric acid of 65wt.%, under 30 ℃ of temperature, corrosion 20min, with the nitric acid in clean alloy surface of deionized water and the hole, get nano-porous gold then;
(2) nano-porous gold is fixed on the glass-carbon electrode, placing concentration is 1mol dm
-3Chlorine palladium acid solution in, soak 10min, allow nano-porous gold metal surface absorption chlorine palladium acid ion;
(3) nano-porous gold that the surface is adsorbed chlorine palladium acid ion places the not solution or the deionized water of metal ion, soaking and washing 10min, the non-metallic ion solution or the deionized water that more renew soak 15min again, repeat 5 times, clean until the nano-porous gold surface clean;
(4) nano porous metal that clean surface has been adsorbed chlorine palladium acid ion places HClO
4In the solution, apply one and carry out the linear scan of current potential to the current potential that can make precious metal ion reduction, make chlorine palladium acid ion be reduced into Pd and be combined in securely on the nano-porous gold hole wall from OCP;
(5) calculate the amount that is modified at the Pd on the nano-porous gold hole wall by the electric weight of chlorine palladium acid ion reduction peak and the valence state of ion; By repeating the number of times of (1)～(4) step, control is modified at the carrying capacity and the structure of the precious metals pd of nanoporous gold surface then.
Claims (6)
1. one kind is carried out the method for coating noble metal to nano-porous gold, is made up of following step:
(1) with thickness is 0.05-1000 μ m, width is 0.1-100cm, length is 0.1-1000cm, it is the nitric acid of 0.1～70wt.% that the electrum that golden amount ratio is 10-40% places concentration, under 0～50 ℃ of temperature, corrosion 1s～1000min with the nitric acid in clean alloy surface of deionized water and the hole, gets nano-porous gold then;
(2) nano-porous gold is fixed on the electrode, placing concentration is 1 μ mol dm
-3～10mol dm
-3The solution that contains precious metal ion in, soak 1s～10h, allow nano-porous gold metal surface absorption precious metal ion;
(3) nano-porous gold that the surface is adsorbed precious metal ion places the not solution or the deionized water of metal ion, soaking and washing 1min-10h, the non-metallic ion solution or the deionized water that more renew soak 1min-10h again, repeat 2-10 time, clean until the nano-porous gold surface clean;
(4) nano porous metal that clean surface has been adsorbed precious metal ion places electrolyte solution, apply one and make the fixed potential of precious metal ion reduction or carry out the linear scan of current potential to the current potential that can make the precious metal ion reduction, make precious metal ion be reduced into precious metal simple substance and also be combined in securely on the nano-porous gold hole wall from OCP;
(5) calculate the amount that is modified at the noble metal on the nano-porous gold hole wall by the electric weight of precious metal ion reduction peak and the valence state of precious metal ion; Then by repeating the number of times of (1)～(4) step, the carrying capacity and the structure of the noble metal of control decorated nanometer porous gold surface.
2. according to claim 1 nano-porous gold is carried out the method for coating noble metal, it is characterized in that: the described electrum of step (1) is that thickness is 0.1-50 μ m, width is 0.5-10cm, and length is 0.5-20cm, and golden amount ratio is 37.5% commercial electrum paper tinsel.
3. according to claim 1 nano-porous gold is carried out the method for coating noble metal, it is characterized in that: the concentration of the described nitric acid of step (1) is 65-68wt.%; Described corrosion temperature is 20～30 ℃; Described etching time is 30min.
4. according to claim 1 nano-porous gold is carried out the method for coating noble metal, it is characterized in that: the solution of the described precious metal ion of step (2) is the solution that contains the inferior palladium acid ion of chloroplatinic acid radical ion, chloroplatinous acid radical ion, chlorine palladium acid ion or chlorine, or the mixed solution of arbitrary volume ratio between them, the concentration of described precious metal ion solution is 1mmol dm
-3, described soak time is 10min.
5. according to claim 1 nano-porous gold is carried out the method for coating noble metal, it is characterized in that: the described electrolyte solution of step (4) is HClO
4Described method of reducing is the current potential linear scan that applies from OCP to relative standard's hydrogen electrode 0V.
6. according to claim 1 nano-porous gold is carried out the method for coating noble metal, it is characterized in that: the described number of repetition of step (5) is 2-5 time.
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| CN101664678B (en) * | 2009-09-18 | 2011-08-17 | 南京大学 | Nanometer material having high-efficiency catalytic activity and preparation method thereof |
| CN101693197B (en) * | 2009-10-19 | 2011-06-22 | 山东大学 | Porous silver catalyzer and process for preparing same |
| CN103149258B (en) * | 2013-02-26 | 2015-09-23 | 山东大学 | A kind of preparation method of the bioelectrode based on nano-porous gold-conducting polymer |
| CN103409780B (en) * | 2013-08-13 | 2016-01-20 | 山东大学 | A kind of method of nano-porous gold being carried out to surface alloy modification |
| CN104419840B (en) * | 2013-09-01 | 2016-11-09 | 济南大学 | Anti-loaded nano porous gold/metal oxide composite and preparation method thereof |
| CN105702966B (en) * | 2014-11-27 | 2018-07-24 | 中国科学院大连化学物理研究所 | A kind of porous material and its preparation and application |
| CN104826625B (en) * | 2015-04-09 | 2017-02-01 | 上海理工大学 | Double-layer TiO2/Au porous structure catalyst and preparation method thereof |
| CN104942281B (en) * | 2015-07-01 | 2016-10-26 | 清华大学 | A kind of porous nanowires of gold and its preparation method and application |
| CN106676575B (en) * | 2015-11-09 | 2018-09-21 | 中国科学院大连化学物理研究所 | A kind of structure of SPE water electrolysis membrane electrode and its preparation and application |
| WO2019002352A1 (en) * | 2017-06-27 | 2019-01-03 | Albert-Ludwigs-Universität Freiburg | Procedure for the manufacturing of nanostructured platinum |
| CN109557042B (en) * | 2018-11-26 | 2021-10-08 | 广东朗研科技有限公司 | Nano-mesoporous metal film plating structure based on semiconductor and terahertz wave enhancement system |
| CN111063805B (en) * | 2019-11-11 | 2021-06-22 | 上海大学 | Organic-inorganic perovskite solar cell and preparation and recovery method |
| CN117476960B (en) * | 2023-12-28 | 2024-02-27 | 潍坊学院 | Nano porous Pt film, preparation method thereof and application thereof in fuel cell electrode |
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