Nanostructured platinum alloys for use as catalyst materials
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
B01J-023/00
B01J-021/00
B01D-050/00
B01D-053/34
C23C-014/00
C23C-014/32
출원번호
US-0784466
(2010-05-20)
등록번호
US-8603400
(2013-12-10)
발명자
/ 주소
Hays, Charles C.
Narayan, Sri R.
출원인 / 주소
California Institute of Technology
대리인 / 주소
Gates & Cooper LLP
인용정보
피인용 횟수 :
1인용 특허 :
26
초록
A series of binary and ternary Pt-alloys, that promote the important reactions for catalysis at an alloy surface; oxygen reduction, hydrogen oxidation, and hydrogen and oxygen evolution. The first two of these reactions are essential when applying the alloy for use in a PEMFC.
대표청구항▼
1. A platinum (Pt) metal containing alloy composition, comprising: a compound including an alloy of Pt and at least one valve metal element A from group IVB or VB of the Periodic table havingan amount of the valve metal; anda structure of the alloy that is single phase, wherein the alloy's surface e
1. A platinum (Pt) metal containing alloy composition, comprising: a compound including an alloy of Pt and at least one valve metal element A from group IVB or VB of the Periodic table havingan amount of the valve metal; anda structure of the alloy that is single phase, wherein the alloy's surface exhibits a catalytic reaction and the alloy's durability is at least as high as: (i) pure Pt exhibiting the catalytic reaction, or(ii) a catalyst consisting essentially of Pt exhibiting the catalytic reaction. 2. The composition of claim 1, wherein the alloy is a film and the film is a continuous film on a nanoparticle support. 3. The composition of claim 1, wherein the alloy is a film and the film is a continuous film on a hollow spherical nanoparticle or nanoshell support. 4. The composition of claim 1, wherein the alloy is a film and the film is a continuous film on a micron-sized metallic or non-metallic support. 5. The composition of claim 1, wherein the alloy is a film and the film is a continuous film on a wire or wire-gauze support. 6. The composition of claim 1, having less than 50% Atomic % of Pt in the alloy. 7. The composition of claim 1, wherein valve metal element A is at least one of Zirconium (Zr), Titanium (Ti), Hafnium (Hf), and Niobium (Nb). 8. The composition of claim 7, wherein the Pt-containing compound further comprises at least one transition metal B, thereby forming a Pt—B-A alloy, and wherein B includes at least one of Cobalt (Co), Nickel (Ni), and Iron (Fe). 9. The composition of claim 8, wherein the Pt-containing compound further comprises at least one platinum group metal (PGM), thereby forming a Pt—PGM-B-A alloy, wherein the PGM element includes at least one of Palladium (Pd), Ruthenium (Ru), Rhodium (Rh), Rhenium (Re), Osmium (Os), and Iridium (Ir). 10. The composition of claim 8, wherein the alloy is (Pt3Co)100-yZry with 0≦y≦30 and y is Atomic %. 11. The composition of claim 8, wherein the alloy is (Pt100-xCox)100-y Zry with 0≦x≦80 and 0.5≦y≦60. 12. The composition of claim 1, wherein the alloy is crystalline. 13. The composition of claim 12, wherein the alloy is nanocrystalline with a grain size of no more than 100 nm. 14. The composition of claim 13, wherein the alloy is nanocrystalline with a grain size of less than 10 nm. 15. The composition of claim 12, wherein the alloy has a (111) crystallographic orientation. 16. The composition of claim 12, wherein the alloy is a film and an amount of A and the amount of Pt in the film is such that the film is electrochemically stable, with no decrease in electrochemical activity of the film, when the electrochemical activity is characterized by conducting multiple cycles of a cyclic voltammogram (CV) over a potential range of 0.0 to at least 1.2 Volts (vs. NHE), to determine the durability of said alloy: measuring a current flowing between the film and an anode, in an electrochemical ½ cell, in response to a voltage applied to the film that is ramped from 0.0 to at least 1.2 Volts at a scan rate of at least 10 mV/second, wherein the voltage is ramped from the 0.0 Volts to the at least 1.2 Volts at least 1000 times (over 1000 cycles); andthe current not varying by more than the measuring's accuracy (+/−10 microamps). 17. The composition of claim 1, wherein the alloy is a cathode in a hydrogen-air fuel cell (H2-Air FC), hydrogen-oxygen fuel cell (H2-O2 FC), or an anode in a direct methanol fuel cell (DMFC), and an amount of A and an amount of Pt in the alloy is such that that the H2-Air FC or H2-O2 FC cathode is at least 2 times more electrochemically active for an oxygen reduction reaction (ORR), than a cathode consisting essentially of Pt,an amount of A and an amount of Pt in the alloy is such that that the H2-Air FC or H2-O2 FC anode is more electrochemically active for the hydrogen oxidation reaction (HOR), than an anode consisting essentially of Pt, oran amount of A and an amount of Pt in the alloy is such that that the DMFC anode is more electrochemically active for the methanol oxidation reaction (MOR), than an anode consisting essentially of Pt. 18. The composition of claim 1, wherein the alloy is a film and the film is crystalline with a grain size such that, when the film is a catalyst for an anode in a hydrogen-air or hydrogen-oxygen fuel cell, a measured Pt-active area (APt) from a hydrogen-oxidation-reaction (HOR) of the anode is greater than that of polycrystalline Pt, or greater than APt=210 μC/cm2. 19. The composition of claim 1, wherein the alloy is a film and amounts of 1 A and Pt are such that the film has a microstructure ranging between a amorphous or nanocrystalline microstructure, or with mixture of both phases. 20. The composition of claim 1, further comprising a nanoparticle including the alloy. 21. The composition of claim 1, further comprising a metallic nanocrystalline cluster or quantum dot on a nanoparticle support, wherein the metallic nanocrystalline cluster or quantum dot includes the alloy. 22. A method of fabricating a platinum (Pt) metal containing alloy composition, comprising: fabricating a compound including an alloy of Pt and at least one valve metal element A, to obtain an amount of the valve metal and a single phase structure of the alloy, wherein the alloy's surface exhibits a catalytic reaction and the alloy's durability is at least as high as: (i) pure Pt, or(ii) a catalyst consisting essentially of Pt. 23. The method of claim 22, wherein the alloy is fabricated by evaporation from multiple targets or from a single alloyed target onto a support (or substrate). 24. The composition of claim 1, wherein: the alloy is disposed within a catalytic converter system for vehicle emissions,the alloy exhibits catalytic properties,the catalytic properties break down harmful byproducts present in hot exhaust streams of the vehicle emissions, including performing one or more of the following reactions:1) reduction of nitrous oxides to nitrogen and oxygen;2) oxidation of carbon monoxide to carbon dioxide; and3) oxidation of unburned hydrocarbon (HCs). 25. A catalytic converter or fuel cell apparatus comprising: an alloy of Pt and at least one valve metal element A from group IVB or VB of the Periodic table havingan amount of the valve metal anda structure of the alloy that is single phase, wherein the alloy's surface exhibits a catalytic reaction in the catalytic converter or fuel cell apparatus and the alloy's durability and catalytic activity is at least as high as: (i) pure Pt exhibiting the catalytic reaction, or(ii) a catalyst consisting essentially of Pt exhibiting the catalytic reaction. 26. The apparatus of claim 25, wherein the apparatus is a catalytic converter and the catalytic reaction breaks down byproducts present in emissions received in the catalytic converter. 27. The apparatus of claim 25, wherein the apparatus is a hydrogen-air fuel cell (H2-Air FC), hydrogen-oxygen fuel cell (H2-O2 FC), or a direct methanol fuel cell (DMFC).
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