WO2012102714A1 - Catalyseur destiné à une pile à combustible et procédé de fabrication correspondant - Google Patents

Catalyseur destiné à une pile à combustible et procédé de fabrication correspondant Download PDF

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Publication number
WO2012102714A1
WO2012102714A1 PCT/US2011/022546 US2011022546W WO2012102714A1 WO 2012102714 A1 WO2012102714 A1 WO 2012102714A1 US 2011022546 W US2011022546 W US 2011022546W WO 2012102714 A1 WO2012102714 A1 WO 2012102714A1
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Prior art keywords
npg
catalyst
platinum
gold
group
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Inventor
Yi Ding
Rong Yue WANG
Shangling TIAN
FanHui MENG
Chaohao HOU
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Blue Nano Inc
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Blue Nano Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H01M4/8621—Porous electrodes containing only metallic or ceramic material, e.g. made by sintering or sputtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8684—Negative electrodes
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the invention belongs to the field of electrochemical technology, and relates to an efficient catalyst and a method for preparing the catalyst with nanoporous structure, in particular, relates to method for preparing a nanoporous gold (NPG) supported platinum surface alloy catalyst with a low platinum loading and high poisoning resistance for fuel cells.
  • NPG nanoporous gold
  • a fuel cell is an energy conversion device that converts the chemical energy of a fuel into electricity through reactions between the fuel and an oxidant with merits such as high efficiency of energy conversion and no pollution.
  • the development of fuel cell technology is particularly urgent in light of the global energy crisis and serious
  • PEMFCs proton exchange membrane fuel cells
  • Direct liquid fuel cells including direct methanol fuel cells and direct formic acid fuel cells, show significant advantages over hydrogen fuel cells in fuel supply. More specifically, direct formic acid fuel cells have great application potential in portable electronic devices such as laptop computers and cell phones, attracting more and more researchers and energy companies' attention due to higher open circuit potential, and less fuel cross over.
  • the high price is one of the key issues to inhibit the wide application of fuel cells.
  • the fuel molecules are oxidized and oxygen is deoxidized on the catalyst in the anode and cathode respectively to convert the chemical energy of the fuel into electrical energy.
  • the fuel cell catalyst platinum with high price is the key issue of fuel cells' high price.
  • traditional method is to prepare the platinum catalyst as a nanoparticle.
  • Amorphous conductive carbon may also be used in the platinum nanoparticle catalysts as a means of support.
  • a catalyst for a fuel cell comprising: a nanoporous gold having one or more coatings of one or more additional metals on its surface, where the additional metals are selected from the group comprising: a group 8 element, a group 10 element, a group 15 element, or a combination thereof, and a method of preparing a catalyst for a fuel cell comprising the steps of: immersing a gold-silver alloy article in a concentrated nitric acid solution to selectively remove silver from the gold-silver alloy article in order to form a nanoporous gold (NPG); rinsing the NPG in deionized water followed by depositing one or more layers of platinum onto the surface of the NPG in order to form an NPG-Pt article; and depositing either bismuth or ruthenium onto the surface of the NPG-Pt article resulting in either an NPG-Pt-Bi or NPG-Pt-Ru catalyst.
  • NPG nanoporous gold
  • FIG.1 illustrates the full cyclic voltammetry (CV) curves of NPG-3Pt inO.IM HCI0 4 .
  • FIG.2 illustrates the full cyclic voltammetry (CV) curves of NPG-3Pt in a mixed solution of 0.1 M HCI0 4 and 0.05M HCOOH.
  • FIG.3 illustrates the full cyclic voltammetry (CV) curves of NPG-3Pt-Bi catalyst in 0.1 M HCI0 4 .
  • FIG.4 illustrates the full cyclic voltammetry (CV) curves of NPG-3Pt-Bi catalyst in a mixed solution of 0.1 M HCI0 4 and 0.05M HCOOH.
  • FIG.5 illustrates the full cyclic voltammetry (CV) curves of NPG-Pt catalyst in 0.5M
  • FIG.6 illustrates the full cyclic voltammetry (CV) curves of NPG-Pt catalyst in a mixed solution of 0.5M H 2 SO 4 and 1 M CH 3 OH.
  • FIG.7 illustrates the full cyclic voltammetry (CV) curves of NPG-Pt-Ru catalyst in 0.5M H 2 SO 4 .
  • FIG.8 illustrates the full cyclic voltammetry (CV) curves of NPG-Pt-Ru catalyst in a mixed solution of 0.5M H 2 S0 4 and 1 M CH 3 OH.
  • FIG.9 illustrates the full cyclic voltammetry (CV) curves of NPG-Pt64 inO.I M
  • FIG.10 illustrates the full cyclic voltammetry(CV) curves of NPG-Pt64 catalyst in a mixed solution of 0.1M HCI0 4 and 1M HCOOH.
  • FIG.11 illustrates the full cyclic voltammetry(CV) curves of NPG-Pt64-Bi catalyst
  • FIG.12 illustrates the full cyclic voltammetry(CV) curves of NPG-Pt64-Bi catalyst in the mixed solution of 0.1 M HCI0 4 and 1 M HCOOH.
  • the present invention is to provide catalysts based on nanoporous gold (NPG) and methods of preparing catalysts for fuel cells, in particular, to provide nanoporous gold supported platinum surface alloy catalysts with low precious metal loading and high poisoning resistance.
  • NPG nanoporous gold
  • one solution is to alloy platinum with some other metal atoms like palladium, bismuth or ruthenium, or to deposit some other metal atoms like bismuth or lead onto the surface of platinum.
  • the chemical or electrochemical corrosion method can be used to prepare nanoporous metal from an alloy of appropriate composition and proportion in order to provide it with large surface area and a controllable, uniform structure.
  • the nanostructure materials can be used as catalysts, and especially as the electricity catalyst support, because of superior properties such as three dimensional nanostructure, continuous pore structure and pore wall, good electrical conductivity, high surface area, and strong corrosion resistance. Karl Sieradzki and R. C. Newman reported a method of forming porous gold structure by electrochemical etching the gold-silver alloy in 1990.( K.
  • the nanoporous gold supported platinum catalyst has the following advantages: 1) the nanoporous metal has a three dimensional, bi-continuous nanoporous structure which favors the conduction of electrons and the diffusion of reactants; 2) platinum is deposited onto the surface of nanoporous gold in the form of atomic layers which has low platinum loading and high utilization; 3) the platinum is combined with the nanoporous gold by metallic bond which has strong structural stability.
  • the oxidation of small organic molecules of fuel should be catalyzed by platinum which is similar to a hydrogen fuel cell.
  • platinum which is similar to a hydrogen fuel cell.
  • the oxidation of small organic molecules in a liquid fuel cell is slow even when catalyzed by platinum, as a poisoning intermediate could be readily formed and inhibit the reaction.
  • the oxidation reaction of methanol on catalytic platinum produces a carbon monoxide intermediate which may be firmly adsorbed on the surface of the catalyst which poisons the catalyst.
  • the oxidation reaction of formic acid on platinum will produce a carbon monoxide intermediate product which poisons the catalyst.
  • a liquid fuel cell anode needs a large amount of catalyst to overcome the over-potential caused by the low catalytic activity and poisoning.
  • Extensive research shows that alloying platinum with other metals or adsorbing an additional metal onto the platinum can greatly reduce the catalyst poisoning during the oxidation of small organic molecules.
  • the poisoning resistance achieved by adding other metals are as follows: 1) accelerate the removal of the carbon monoxide poisoning intermediate through a bi-functional mechanism; 2) improve the catalytic activity of platinum by altering the electronic structure; 3) reduce the poisoning intermediate formation by changing the atomic ensemble of platinum and the path of the reaction.
  • the present invention prepares the NPG supported platinum surface alloy catalyst using a surface modification method.
  • the NPG supported platinum surface alloy catalyst not only maintains the advantages of an NPG supported platinum catalyst such as good electrical conduction, high platinum utilization and good stability; it also solves the problem of catalyst poisoning.
  • the present invention shows that, the methods of preparing a NPG supported platinum catalyst after de-alloying gold and silver alloys to get the nanoporous gold include: 1) surface ion adsorption combined with electrochemical reduction, or 2) under potential deposition (UPD) combined with in-situ replacement, or 3) the platinum deposited on nanoporous gold surface using hydrazine vapor reduction method to form the catalyst.
  • UPD under potential deposition
  • the present invention controls a catalyst's catalytic activity by adjusting the platinum loading by methods of: a) regulating the cycles of adsorption deposition, b) regulating the cycles of UPD combined with in-situ replacement, or c) regulating the time of reduction in hydrazine vapor; and adjusting the bismuth or ruthenium loading by regulating the deposition potential and deposition time (or soaking time).
  • a catalyst is a substance which modifies and/or increases the rate of a reaction without being consumed in the process. At present, it is necessary to greatly reduce the amount of group 10 elements and group 11 elements which are incorporated into a catalyst in order for fuel cells to achieve economic viability.
  • NPG nanoporous gold
  • a catalyst may refer to an anode catalyst. In another embodiment of the present invention, a catalyst may refer to a cathode catalyst or cathodic catalyst.
  • fuel cell refers to an electrochemical device that converts the chemical energy of a fuel, along with an oxidant, into electrical energy.
  • Afuel cell is different from a battery in that a fuel cell can continuously supply energy so long as fuel is supplied to the cell.
  • the fuel and the oxidant usually oxygen, are supplied continuously to a fuel cell from an external source.
  • the fuel and oxidant are contained within and when the reactants have been consumed, the battery must either be replaced or recharged.
  • One or more membrane electrode assemblies (MEAs) are contained within a fuel cell. Two chemical reactions occur at the interfaces of the three different segments (anode, cathode and electrolyte).
  • the net result of the two reactions is that fuel is consumed, water or carbon dioxide is created, and an electric current is created, which can be used to power electrical devices.
  • a catalyst oxidizes the fuel which turns the fuel into a positively charged ion, a negatively charged electron, and carbon dioxide.
  • the PEM or electrolyte is a substance specifically designed so ions can pass through it, but the electrons cannot.
  • the freed electrons travel through a wire creating the electric current.
  • the ions travel through the electrolyte to the cathode. Once reaching the cathode, the ions are reunited with the electrons and the two react with a third chemical, usually oxygen, to create water.
  • fuel cells can be combined in series and/or parallel circuits.
  • the fuel cell is a proton exchange membrane fuel cell. In another embodiment of the present invention, the fuel cell is a direct formic acid fuel cell.
  • NPG refers to nanoporous gold, which are prepared according the present invention.
  • NPG refers to a nanoporous gold.
  • NPG refers to a plurality of particles containing nanostructure gold.
  • NPG-3Pf refers to an NPG with three deposition cycles of platinum deposited onto its surface by electrochemical linear scanning from the open circuit potential to the negative potential.
  • platinum is deposited onto a NPG catalyst from the open circuit potential to 0.3V (versus standard hydrogen electrode) by 50mV/s three times according to the present invention resulting in an NPG-3 Pt catalyst.
  • NPG-3Pt-Bi refers to an NPG-3Pt catalyst with a layer of bismuth deposited onto its surface by under potential deposition.
  • bismuth is deposited onto the surface of an NPG-3Pt catalyst at 0.2V (versus standard hydrogen electrode) for 400 seconds according to the present invention resulting in an NPG-3 Pt-Bi catalyst.
  • NPG-Pt refers to an NPG with one deposition cycle of platinum deposited onto its surface by electrochemical linear scanning from the open circuit potential to the negative potential, according to the process of the present invention.
  • a one deposition cycle of platinum is deposited onto the surface of an NPG from the open circuit potential to 0.3V (versus standard hydrogen electrode) by 50mV/s one time according to the present invention resulting in an NPG-Pt catalyst.
  • NPG-Pt-Ru refers to an NPG-Pt catalyst with a layer of ruthenium deposited onto its surface by copper (Cu) under potential deposition (UPD).
  • Cu copper
  • UPD potential deposition
  • ruthenium is deposited onto the surface of an NPG-Pt catalyst at 0.2V (versus standard hydrogen electrode) for 400 seconds according to the present invention resulting in an NPG-1 Pt-Ru catalyst.
  • NPG-Pt64 refers to a NPG onto which platinum has been deposited for 64 minutes through the use of the hydrazine vapor reduction method according to the present invention.
  • NPG-Pt64-Bi refers to an NPG-Pt64 catalyst with a layer of bismuth deposited onto its surface by under potential deposition.
  • bismuth is deposited onto the surface of an NPG-Pt64 catalyst at 0.3V (versus standard hydrogen electrode) for 400 seconds according to the present invention resulting in an NPG-Pt64-Bi catalyst.
  • Group 8 elements includes iron, ruthenium and osmium.
  • Group 10 elements includes nickel, palladium and platinum.
  • Group 11 elements includes copper, silver and gold.
  • Group 15 elements includes nitrogen, phosphorus, arsenic, antimony and bismuth.
  • a 0.05 -50 atomic layer platinum has thickness of 0.01-500nm. Additionally, different atomic layers of platinum have corresponding platinum loading. In one embodiment of the present invention, 0.05 -50 atomic layer platinum has thickness of 0.25-1 Onm, because platinum has a certain atomic radius, a 0.05 atomic layer of platinum still has a thickness of the atomic radius. In another embodiment of the present invention, the loading does not reach one atomic layer, that is to say, platinum does not cover with the NPG completely. In another embodiment of the present invention, a 0.05 -20 atomic layer platinum has thickness of 0.25-4nm. In still another embodiment of the present invention, a 0.05 -5 atomic layer platinum has thickness of 0.25-1 nm.
  • a coverage of 0.01-0.99 refers to a surface coverage of one material (e.g. NPG or Pt) by another material (e.g. Bi or Ru) of between 1 % and 99%. In one embodiment, the coverage may be between 0.05 and 0.80. In another
  • the coverage may be between 0.1 and 0.65. In still another embodiment, the coverage may be between 0.20 and 0.50. Also in the present invention, a 0.01-0.99 atomic layer bismuth or ruthenium has thickness of 0.0025-0.5nm. Additionally, different atomic layers of bismuth or ruthenium have corresponding bismuth or ruthenium loading. In one embodiment of the present invention, a 0.01-0.99 atomic layer bismuth or ruthenium has thickness of about 0.25nm, because bismuth and ruthenium each have a certain atomic radius, a 0.05 atomic layer of bismuth or ruthenium still has a thickness of each atomic radius respectively.
  • the loading of either bismuth or ruthenium does not reach one atomic layer, that is to say, neither bismuth nor ruthenium cover the NPG completely.
  • the 0.01-0,99 atomic layer of either bismuth or ruthenium will not reach one atom layer, because if they cover with platinum, the platinum is unable to display it's superior catalytic activity.
  • the present invention discloses a catalyst for a fuel cell comprising a nanoporous gold having one or more coatings of one or more additional metals selected from the group comprising: a group 8 element, a group 10 element, a group 15 element, or a combination thereof on its surface.
  • the Group 8 elements include ruthenium
  • the Group 10 elements include platinum
  • the Group 15 elements include bismuth.
  • the catalyst for a fuel cell includes a catalyst comprised of a nanoporous gold, one or more layers of platinum bonded to the surface of the nanoporous gold and less than one layer of bismuth or less than one layer of ruthenium bonded to the surface of the platinum.
  • the catalyst described above may possess the following characteristics: a thickness of 0.05-50pm; a width of 0.1 -100cm; a length of 0.2-1000cm; and a three dimensional nanoporous gold structure having an atomic layer of platinum with a uniform thickness of 0.05-50 bonded to its surface and a layer of bismuth atoms having a coverage of 0.01-0.99 or a layer of ruthenium atoms having a coverage of 0.01-0.99 bonded to the layer of platinum.
  • the membrane electrode assembly as described above may be for use in a direct formic acid fuel cell.
  • the present invention discloses another catalyst for a fuel cell comprising: a nanoporous gold having one or more coatings of one or more additional metals selected from the group comprising: a group 8 element, a group 10 element, a group 11 element, a group 15 element, or a combination thereof on its surface.
  • the group 8 elements include ruthenium
  • the group 10 elements include platinum
  • the group 11 elements include silver and gold
  • the group 15 elements include bismuth.
  • the catalyst for a fuel cell is comprised of a nanoporous gold, one or more layers of platinum bonded to the surface of the nanoporous gold and less than one layer of either bismuth or ruthenium bonded to the surface of the platinum.
  • the catalyst may possess the following characteristics: a thickness of
  • the catalyst for a fuel cell may be an anode catalyst.
  • a catalyst may be an NPG-Pt-Bi catalyst or an NPG-Pt-Ru catalyst.
  • the gold-silver alloy article may be in the range of 0.2-1000 cm long, 0.1-100 cm wide, 0.05-50 urn thick, and 10-60% gold (wt.%).
  • the gold-silver alloy article has a thickness of IOOnm- ⁇ ⁇ , a width of 1-10cm, and a length of 2-15cm, and comprising 20-50% gold (wt.%).
  • a layer of platinum having a thickness of 0.01 -500nm may be deposited onto the surface of the NPG.
  • a layer of platinum having a thickness of 0.25-1 Onm may be deposited onto the surface of the NPG.
  • the anode catalyst may be a catalyst ranging from a NPG-Pt1-Bi to a NPG-Pt1000-Bi. In another embodiment, the anode catalyst may be a catalyst ranging from a NPG-Pt1-Bi to a NPG-Pt500-Bi. In still another embodiment, the anode catalyst may be a catalyst ranging from a NPG-Pt5-Bi to a NPG-Pt100-Bi. In yet another embodiment, the anode catalyst may be a catalyst ranging from a NPG-Pt10-Bi to a NPG-Pt50-Bi. In another embodiment, the anode catalyst may be a NPG-Pt64-Bi catalyst. In still another embodiment, the anode catalyst may be a NPG-Pt16-Bi catalyst. In yet another embodiment, the anode catalyst may be a
  • the anode catalyst may be a catalyst ranging from a NPG-Pt1-Ru to a NPG-Pt1000-Ru. In another embodiment, the anode catalyst may be a catalyst ranging from a NPG-Pt1-Ru to a NPG-Pt500-Ru. In still another embodiment, the anode catalyst may be a catalyst ranging from a NPG-Pt 5-Ru to a NPG-Pt100-Ru. In yet another embodiment, the anode catalyst may be a catalyst ranging from a NPG-Pt10-Ru to a NPG-Pt50-Ru.
  • the anode catalyst may be a NPG-Pt64-Ru catalyst. In still another embodiment, the anode catalyst may be a NPG-Pt16-Ru catalyst. In yet another embodiment, the anode catalyst may be a NPG-Pt8-Ru catalyst.
  • the anode catalyst may be a catalyst ranging from a NPG-1 Pt-Bi catalyst to a NPG-1 OOPt-Bi catalyst. In yet another embodiment, the anode catalyst may be a catalyst ranging from a NPG-3Pt-Bi catalyst to a NPG-8Pt-Bi catalyst. In still another embodiment, the anode catalyst may be a
  • the anode catalyst may be a
  • the anode catalyst may be a
  • the anode catalyst may be a
  • the anode catalyst may be a catalyst ranging from a NPG-1 Pt-Ru catalyst to a NPG-1 OOPt-Ru catalyst. In yet another embodiment, the anode catalyst may be a catalyst ranging from a NPG-3Pt-Ru catalyst to a NPG-8Pt-Ru catalyst. In still another embodiment, the anode catalyst may be a NPG10Pt-Ru catalyst. In yet another embodiment, the anode catalyst may be a
  • the anode catalyst may be a
  • the anode catalyst may be a
  • the present invention also discloses a method of preparing a catalyst for a fuel cell comprising the steps of: immersing or placing a gold-silver alloy article in a concentrated nitric acid solution to selectively remove silver from the gold-silver alloy article in order to form a nanoporous gold (NPG); rinsing the NPG in deionized water followed by depositing one or more layers of platinum onto the surface of the NPG wherein the layers of platinum ranging in thickness from sub-monoatomic to a plurality of monoatomic or atomic layers in order to form an NPG-Pt article; and depositing either bismuth or ruthenium onto the surface of the NPG-Pt article resulting in a catalyst, and more specifically an NPG-Pt-Bi catalyst or an NPG-Pt-Ru catalyst.
  • the present invention includes the preparation methods of making various nanoporous gold supported platinum catalysts by de-alloying gold and silver alloys to obtain a nanoporous gold, which is then modified by methods which include: (i) surface ion adsorption combined with electrochemical reduction, (ii) under potential deposition (UPD) combined with in-situ replacement, (iii) using a chloroplatinic ion and hydrazine vapor reduction method to deposit the platinum onto the surface of the nanoporous gold, or a combination thereof.
  • the nanoporous gold supported platinum catalyst is then immersed in a perchloric acid solution containing bismuth ion or ruthenium ion to form the Bi-modified or Ru-modified nonporous gold catalyst supported platinum catalyst.
  • a gold-silver alloy article is used.
  • the method described above includes a gold-silver alloy article which is 0.2-1000 cm long, 0.1-100 cm wide, 0.05-50 urn thick, and 10-60% gold (wt.%).
  • the gold-silver alloy article may have a thickness of 100nm-1 pm, a width of 1-10cm, and a length of 2-15cm, and comprising 50% gold (wt.%).
  • a concentrated nitric acid solution is used.
  • the method described above includes a gold-silver alloy article being immersed in concentrated nitric acid for a time period ranging from 0.1 to 1000 minutes at a temperature in the range of 0 to 60°C. In another embodiment of the present invention, the method described above includes a gold-silver alloy article being immersed in concentrated nitric acid for a time period ranging from 15 to 60 minutes at a temperature in the range of 20-40°C.
  • a layer of platinum may be deposited onto the NPG using a method selected from the group comprising: (1) a surface ion adsorption combined with electrochemical reduction method; (2) an under potential deposition method combined with in-situ replacement; (3) a chloroplatinic ion and hydrazine vapor method; or (4) a combination thereof.
  • the surface ion adsorption combined with electrochemical reduction method may be utilized for different thicknesses of NPG wherein a layer of platinum is deposited ranging in thickness from sub-monoatomic to a plurality of atomic layers, and for large platinum loading, the NPG can be adsorbed and deposit directly in a chloroplatinic ion or chloroplatinous ion solution; or for option (2) the under potential deposition method combined with in-situ replacement may be utilized to deposit a layer of platinum having a thickness of 50-500nm onto the surface of NPG; or for option (3) the chloroplatinic ion and hydrazine vapor method may be utilized to deposit a layer of platinum having a thickness of less than 100nm onto the surface of NPG.
  • the concentration of chloroplatinic ion or chloroplatinous ion in option (1) is preferably 0.001 -lOOOOmM, the NPG is placed into the chloro
  • the chloroplatinous ion solution in option (3) has a concentration in the range of 0.1 - 10g/L, has an pH value of between 8-11 and the NPG is exposed to the hydrazine.vapor for a period of time ranging from 1- 000 minutes.
  • the concentration of chloroplatinic ion or chloroplatinous ion in option (1) is preferably 0.5-1 OmM
  • the NPG is placed into the chloroplatinic ion or chloroplatinous ion solution for a soaking time period in the range of 3-30 minutes and a cleaning step to rinse the chloroplatinic ion or chloroplatinous ion solution from the NPG is completed between 3 and 6 times.
  • the concentration of the chloroplatinic ion solution in option (3) is 1g/L
  • the pH value of the chloroplatinic ion solution is 10
  • the period of time the NPG is exposed to the hydrazine vapor is in the range of 5-60 minutes.
  • the method described above includes the process of depositing bismuth or ruthenium onto the surface of a NPG-Pt article.
  • This deposition may be accomplished by any methods known in the art.
  • bismuth or ruthenium is deposited onto the surface of a NPG-Pt article by placing the NPG-Pt article into a perchloric acid solution containing 0.1 - 1 OOmM bismuth or ruthenium and adding a 0-0.5V potential (versus standard hydrogen electrode) to the NPG-Pt article for a deposition time period of 1-1000 minutes to obtain an NPG-Pt-Bi catalyst or an
  • NPG-Pt-Ru catalyst In another embodiment of the present invention, bismuth or ruthenium is deposited onto the surface of a NPG-Pt article by placing the NPG-Pt article into a perchloric acid solution containing 0.1 - 100mM bismuth or ruthenium and soaking the NPG-Pt article for a soaking time period of 1-1000 minutes to obtain an NPG-Pt-Bi catalyst or an NPG-Pt-Ru catalyst.
  • the concentration of the chloroplatinic ion or chloroplatinous ion solution is 0.5-5mM.
  • the concentration of the perchloric acid solution containing Bi or Ru is 3-5mM
  • the deposition potential is 0.2-0.4V (versus standard hydrogen electrode)
  • the deposition time period is 5-10 minutes or the soaking time period is 5-10 minutes.
  • the present invention also describes another method of preparing a catalyst for a fuel cell comprising the steps of: immersing a gold-silver alloy article in a concentrated nitric acid solution to selectively remove silver from the gold-silver alloy article in order to form a nanoporous gold (NPG); rinsing the NPG in deionized water followed by depositing one or more layers of one or more additional metals onto the surface of the NPG, where the additional metals are selected from the group comprising: a group 8 element, a group 10 element, a group 15 element, or a combination thereof; and the layers of additional metals range in thickness from sub-monoatomic to a plurality of monoatomic or atomic layers in order to form the catalyst.
  • NPG nanoporous gold
  • the group 8 elements include ruthenium; the group 10 elements include palladium and platinum and the group 15 elements include bismuth.
  • the catalyst is comprised of a nanoporous gold, one or more layers of platinum bonded to the surface of the
  • the catalyst has the following characteristics: a thickness of 0,05-50pm; a width of 0.1 -100cm; a length of 0.2-1000cm; and a three dimensional nanoporous gold structure having an atomic layer of deposited platinum with a 0.05-50 atomic layer thickness bonded to its surface and a layer of bismuth or ruthenium having a coverage of 0.01-0.99 bonded to the nanoporous gold and/or the layer of platinum.
  • the present invention can control the catalyst support's surface area by adjusting the thickness and pore size of the nanoporous gold.
  • the present invention can control a catalyst's catalytic activity by adjusting the platinum loading by methods which include: i) regulating the cycle of adsorption deposition, ii) regulating the cycle of UPD combined with in-situ replacement, or iii) regulating the time of reduction in hydrazine vapor.
  • the present invention can also control a catalyst's catalytic activity by controlling the amount of platinum deposited onto the NPG and by adjusting the bismuth or ruthenium loading by regulating the deposition potential and deposition time period (or soaking time period).
  • the method of depositing sub-monoatomic layer of bismuth or ruthenium on the surface of nanoporous gold supported platinum catalyst uses electrochemical or adsorption deposition. It is simple, controllable, and can control the catalytic activity of catalyst by easily regulating the deposition potential and deposition time to adjust the bismuth or ruthenium loading.
  • the advantages of either Bi-modified or Ru-modified NPG-Pt catalysts with low precious metal loading for direct formic acid fuel cell anode include the following: (1) NPG has superior electron transfer ability and superior chemical and electrochemical corrosion resistance than a traditional fuel cell catalyst;
  • NPG can easily be made into a membrane structure which is compatible with the fuel cell electrolyte membrane, thus NPG is a better catalyst support.
  • a platinum catalyst can be bonded to the surface of NPG with a sub-atomic layer or a plurality of atomic layers by methods which include i) surface ion adsorption combined with electrochemical reduction, or ii) under potential deposition (UPD) combined with in-situ replacement, or iii) reduction in hydrazine vapor, greatly improving the utilization of platinum catalyst;
  • a Bi-modified or Ru-modified NPG-Pt catalyst can decrease the precious metal loading by about an order of magnitude while maintaining the same discharge level, and also decrease the platinum loading by about two orders of magnitude
  • a 9K gold-silver alloy sample (1.2 cm long, 1 cm wide, 100 nm thick) was placed in concentrated nitric acid for 120 minutes at 20°C to form a nanoporous gold (NPG) which was then rinsed and cleaned in deionized water.
  • NPG nanoporous gold
  • NPG-3Pt catalyst The NPG was placed in 1mM H 2 PtCI 6 solution for 5 minutes followed by a cleaning in deionized water. Platinum was then deposited onto the surface of the NPG using the electrochemical reduction method. This process is repeated 3 times to obtain a NPG-3Pt catalyst.
  • NPG-3Pt catalyst was placed in 0.1M HCI0 4 solution containing 3mM bismuth (Bi), in order to deposit Bi onto the surface of the NPG-3Pt catalyst by soaking for 5 minutes to form a NPG-3Pt-Bi catalyst.
  • the full CV curves of NPG-3Pt-Bi catalyst were shown in FIG.3 and the electrochemical catalytic activity of NPG-3Pt-Bi catalyst for HCOOH was shown in FIG.4.
  • FIG1 illustrates the full cyclic voltammetry (CV) curves of an NPG-3Pt catalyst in 0.1 M HCI0 ,made by de-alloying a 9 karat (K), 100 nm thick Ag-Au alloy in 68%(wt.%) nitric acid for 120 minutes at 20°C resulting in an NPG, followed by subjecting the NPG to platinum adsorption-deposition 3 times to obtain the NPG-3P1
  • the curve shows that, the platinum begins to oxidize around 0.8V, the platinum reduction peak is around 0.75V during the backward scan, and hydrogen under potential adsorption-desorption peaks at the platinum surface are between 0.05-0.4V. It is clear that the platinum has been deposited onto the surface of the nanoporous gold.
  • FIG.2 illustrates the full cyclic voltammetry (CV) curves of NPG-3Pt catalyst in a mixed solution of 0.1 M HCI0 4 and 0.05M HCOOH.
  • the HCOOH oxidation starting peak position and the oxidation peak position are relatively low, which shows the adsorption depositing samples have high catalytic activity and good poisoning resistance.
  • FIG.3 illustrates the full cyclic voltammetry (CV) curves of an NPG-3Pt-Bi catalyst in 0.1 M HCIO 4 , made by de-alloying a 9 karat (K), 100 nm thick Ag-Au alloy in 68%(wt.%) nitric acid for 120 minutes at 20°C resulting in an NPG, followed by subjecting the NPG to platinum adsorption-deposition 3 times to obtain the NPG-3Pt, followed by once deposition of Bi onto the surface of the platinum.
  • K 9 karat
  • FIG.4 illustrates the full cyclic voltammetry (CV) curves of an NPG-3Pt-Bi catalyst in a mixed solution of 0.1 M HCI0 4 and 0.05M HCOOH.
  • CV cyclic voltammetry
  • a 12K gold-silver alloy sample (1.2 cm long, 1 cm wide, 100 nm thick) was placed in concentrated nitric acid for 30 minutes at 30°C to form a nanoporous gold (NPG) which was then rinsed and cleaned in deionized water;
  • NPG-Pt catalyst was placed in a mixed solution of 1 mM ruthenium and 0.1 M HCIO 4 and soaked for 10 seconds in order to deposit Ru onto the surface of the NPG-Pt catalyst to form a NPG-Pt-Ru catalyst with low precious metal loading for fuel cell.
  • the full CV curves of NPG-Pt-Ru catalyst were shown in FIG.7 and the electrochemical catalytic activity of NPG-Pt-Ru catalyst for CH 3 OH was shown in FIG.8.
  • FIG.5 illustrates the full cyclic voltammetry (CV) curves of an NPG-Pt catalyst in 0.5M H2SO4, which was made by de-alloying a 12 karat (K), 100 nm thick Ag-Au alloy in 68%(wt.%) nitric acid for 30 min at 30°C resulting in an NPG, followed by subjecting the NPG to under potential deposition(UPD) of copper (Cu) and platinum replacement.
  • the curve shows that, the platinum begins to oxidize around 0.8V, the platinum reduction peak is around 0.75V during the backward scan, and hydrogen under potential
  • adsorption-desorption peaks at the platinum surface are between 0.05-0.4V. It is clear that the platinum has been deposited onto the surface of the nanoporous gold.
  • FIG.6 illustrates the full cyclic voltammetry (CV) curves of an NPG-Pt catalyst in a mixed solution of 0.5M H 2 S0 4 and 1 M CH 3 OH which was made by de-alloying a 12 karat (K), 100 nm thick Ag-Au alloy in 68%(wt.%) nitric acid for 30 min at 30°C resulting in an NPG, followed by subjecting the NPG to under potential deposition(UPD) of copper (Cu) and platinum replacement.
  • the curves show that the CH 3 OH oxidation onset potential is around 0.6V and the large current density, normalized to the platinum quality, shows the high utilization of platinum.
  • FIG.7 illustrates the full cyclic voltammetry (CV) curves of an NPG-Pt-Ru catalyst in 0.5M H 2 S0 4 , which was prepared by de-alloying a 12 karat (K), 100 nm thick Ag-Au alloy in 68%(wt.%) nitric acid for 30 min at 30°C resulting in an NPG, followed by subjecting the NPG to under potential deposition(UPD) of copper (Cu) and platinum replacement followed by once deposition of ruthenium.
  • the curves show that around 0.05-0.4V the hydrogen under potential adsorption-desorption peaks become decrescent, around 0.4-0.6V the electric double layer grows wider and the oxidation peak becomes large. This shows that ruthenium has been successfully deposited onto the surface of the platinum.
  • FIG.8 illustrates the full cyclic voltammetry (CV) curves of an NPG-Pt-Ru catalyst in a mixed solution of 0.5M H 2 S0 4 and 1 M CH 3 OH, which was prepared by de-alloying a 12 karat (K), 100 nm thick Ag-Au alloy in 68%(wt.%) nitric acid for 30 min at 30°C resulting in an NPG, followed by subjecting the NPG to under potential deposition(UPD) of copper (Cu) and platinum replacement followed by once deposition of ruthenium.
  • the curves show that the methanol oxidation peak is around 0.5V, though the current density normalized to platinum quality decreases, the methanol starting peak position is forward about 100mV. This shows the nanoporous gold supported platinum catalyst modified with ruthenium has higher catalytic activity and higher carbon monoxide poisoning resistance capability in the process of methanol oxidation.
  • FIG.9 illustrates the full cyclic voltammetry (CV) curves of a sample in 0.1 M HCI0 4 , where the sample has an NPG-Pt64 catalyst which was made by de-alloying a 12 karat (K), 100 nm thick Ag-Au alloy in 68%(wt.%) nitric acid for 15 min at 30°C resulting in an NPG, followed by placing the NPG in a 1g/L H 2 PtCI 6 solution (pH value is 10), in order to deposit platinum onto the surface of the NPG in N 2 H 4 vapor for 64 minutes to form an NPG-Pt64 catalyst.
  • K 12 karat
  • pH value is 10
  • the curve shows that the platinum begins to oxidize around 0.8V, the platinum reduction peak is around 0.8V during the backward scan, and hydrogen under potential deposition (UPD) adsorption-desorption peaks at the platinum surface are between 0.05-0.4V. This shows that platinum has been successfully deposited onto the surface of the NPG.
  • FIG.10 illustrates the full cyclic voltammetry (CV) curves of a platinum decorated NPG(NPG-Pt64) catalyst in a mixed solution of 0.1 M HCI0 4 and 1 M HCOOH where the currents have been normalized to the geometrical areas of the samples.
  • a 12K gold-silver alloy sample (1.2 cm long, 1 cm wide, 100 nm thick) was immersed in concentrated nitric acid for 15 minutes to selectively dissolve silver from the alloy to form a nanoporous gold (NPG) which was then rinsed and cleaned in deionized water;
  • NPG-Pt64 catalyst was placed in 0.1 M HCI0 solution containing 3mM bismuth (Bi), in order to deposit Bi onto the surface of the NPG-Pt64 catalyst by adding 0.4V potential(versus standard hydrogen electrode) for 400 seconds to form a
  • NPG-Pt64-Bi catalyst The full CV curves of the NPG-Pt64-Bi catalyst are shown in FIG.11 and the electrochemical catalytic activity of the NPG-Pt64-Bi catalyst for HCOOH is shown in FIG.12.
  • FIG.11 illustrates the full cyclic voltammetry (CV) curves of the Bi-modified nanoporous gold supported platinum catalyst (NPG-Pt64-Bi) in 0.1 M HCI0 4 .
  • the catalyst was made by under potential depositing (UDP) Bi on the surface of the nanoporous gold supported platinum at 0.4V (versus standard hydrogen electrode) for 400 seconds.
  • UDP under potential depositing
  • the curve shows that hydrogen UPD adsorption-desorption peaks were covered by the deposition of Bi.
  • the Bi oxidation peak at 1 V and the reduction peak at 0.4V shows that Bi has been deposited on the nanoporous gold supported platinum catalyst successfully to form the Bi-modification nanoporous gold supported platinum catalyst (NPG-Pt64-Bi).
  • FIG.12 illustrates the full cyclic voltammetry (CV) curves of a sample with an NPG-Pt64-Bi catalyst in a mixed solution of 0.1 M HCIO 4 and 1 M HCOOH, where the currents have been normalized to the geometrical areas of the samples.
  • the higher oxidation current during the forward scan and backward scan compared to the NPG-Pt64 catalyst show that the NPG-Pt64-Bi catalyst displays higher catalytic activity.
  • the almost coincident oxidation current during the forward scan compared to the backward scan peaks shows that the NPG-Pt64-Bi catalyst would not be easily poisoned by CO.
  • a 12K gold-silver alloy sample (1.3 cm long, 1 cm wide, 1 ⁇ thick) was placed in concentrated nitric acid for 120 minutes at 30°C to form a nanoporous gold (NPG) which was then rinsed and cleaned in deionized water;
  • NPG-10Pt catalyst was placed in a 1 mM H 2 PtCI 6 solution for 5 minutes for adsorbing followed by a cleaning in deionized water. Platinum was then deposited onto the surface of the NPG using the electrochemical reduction method. This process is repeated 10 times to obtain a NPG-10Pt catalyst.
  • NPG-10Pt catalyst was placed in 0.1 M HCI0 4 solution containing 3mM bismuth (Bi) in order to deposit Bi onto the surface of the NPG-10Pt catalyst by adding 0.4V potential (versus standard hydrogen electrode) for 400 seconds to form a
  • NPG-10Pt-Bi catalyst with low precious metal loading for fuel cell NPG-10Pt-Bi catalyst with low precious metal loading for fuel cell.

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Abstract

L'invention concerne un catalyseur destiné à une pile à combustible qui comprend: de l'or nanoporeux possédant un ou plusieurs revêtements d'un ou plusieurs métaux supplémentaires sur sa surface, ces métaux étant sélectionnés parmi le groupe comprenant: un élément de groupe (8), un élément de groupe (10), un élément de groupe (15), ou une combinaison de ceux-ci, et un procédé de préparation d'un catalyseur pour une pile à combustible qui comprend les étapes consistant: à immerger un article en alliage or-argent dans une solution d'acide nitrique concentrée pour sélectivement éliminer l'argent de l'article afin de former un or nanoporeux (NPG); à rincer le NPG dans de l'eau désionisée puis à déposer une ou plusieurs couches de platine sur la surface du NPG afin de former un article NPG-Pt; et à déposer soit du bismuth soit du ruthénium sur la surface de l'article NPG-Pt ce qui produit soit un NPG-Pt-Bi soit un catalyseur NPG-Pt-Ru.
PCT/US2011/022546 2011-01-26 2011-01-26 Catalyseur destiné à une pile à combustible et procédé de fabrication correspondant Ceased WO2012102714A1 (fr)

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US20180354232A1 (en) * 2017-06-09 2018-12-13 Tsinghua University Method for making composite structure with porous metal
CN109599580A (zh) * 2018-12-24 2019-04-09 天津理工大学 一种用于纯液体燃料电池的超薄膜电极及其制备方法和应用
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US20040229077A1 (en) * 2003-05-14 2004-11-18 Akihito Mori Plated material and method of manufacturing the same, terminal member for connector, and connector
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WO2018215413A1 (fr) * 2017-05-24 2018-11-29 Centre National De La Recherche Scientifique Procede de preparation d'une membrane conductrice, transparente et flexible
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US11192337B2 (en) * 2017-06-09 2021-12-07 Tsinghua University Method for making composite structure with porous metal
CN109599580A (zh) * 2018-12-24 2019-04-09 天津理工大学 一种用于纯液体燃料电池的超薄膜电极及其制备方法和应用
CN118156530A (zh) * 2024-01-31 2024-06-07 天津大学 一种基于纳米多孔金薄膜的柔性燃料电池及其制备方法

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