CN101808735B - 催化剂 - Google Patents
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- CN101808735B CN101808735B CN200880100306.7A CN200880100306A CN101808735B CN 101808735 B CN101808735 B CN 101808735B CN 200880100306 A CN200880100306 A CN 200880100306A CN 101808735 B CN101808735 B CN 101808735B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 125
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 53
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 26
- 239000000956 alloy Substances 0.000 claims abstract description 26
- 229910001260 Pt alloy Inorganic materials 0.000 claims abstract description 9
- 239000000446 fuel Substances 0.000 claims description 25
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- 229910052707 ruthenium Inorganic materials 0.000 claims description 24
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- 229910052718 tin Inorganic materials 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000012876 carrier material Substances 0.000 claims description 4
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- 125000004429 atom Chemical group 0.000 description 8
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- -1 is supplied to anode Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
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- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- CVOFKRWYWCSDMA-UHFFFAOYSA-N 2-chloro-n-(2,6-diethylphenyl)-n-(methoxymethyl)acetamide;2,6-dinitro-n,n-dipropyl-4-(trifluoromethyl)aniline Chemical compound CCC1=CC=CC(CC)=C1N(COC)C(=O)CCl.CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O CVOFKRWYWCSDMA-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
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- 229920000297 Rayon Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
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- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
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- 150000004678 hydrides Chemical class 0.000 description 1
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- YLPJWCDYYXQCIP-UHFFFAOYSA-N nitroso nitrate;ruthenium Chemical compound [Ru].[O-][N+](=O)ON=O YLPJWCDYYXQCIP-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
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- 239000010703 silicon Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
-
- 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
- H01M4/921—Alloys or mixtures with metallic elements
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inert Electrodes (AREA)
- Catalysts (AREA)
Abstract
公开了一种铂合金催化剂PtX，其中铂在所述本体合金中的原子百分比为5～50at％，余量为X，其特征在于铂在所述合金表面的原子百分比为10～80at％，余量为X，条件是铂在所述合金表面的at％比铂在所述本体合金中的at％高至少25％。
Description
本发明涉及新的铂合金催化剂，和该催化剂的用途，尤其是在燃料电池如直接甲醇燃料电池中的用途，其中铂在所述合金表面的原子百分比大于铂在本体合金组合物中的原子百分比。
燃料电池为电化学电池，包括由电解质分隔开的两个电极。燃料，例如氢、诸如甲醇或乙醇等醇，或者氢化物，被供应给阳极，而氧化剂，例如氧气或空气，被供应给阴极。在电极处发生电化学反应，而且燃料和氧化剂的化学能被转化为电能和热量。使用电催化剂来促进燃料在阳极的电化学氧化和氧气在阴极的电化学还原。
用于燃料氧化和氧气还原的电催化剂通常基于铂或者与一种或多种其他金属合金化的铂。铂合金可以被用作高表面积金属黑(未负载催化剂)或者可以被沉积到导电碳衬底(负载催化剂)上。
铂是一种昂贵的金属，因此理想地是降低铂在电催化剂中的比例，同时维持或者改善催化活性。本发明人已经设法提供与已知催化剂相比具有类似或者改进的活性，但具有较低铂含量的改进的铂催化剂。
因此，本发明提供铂合金催化剂PtX，其中铂在本体合金中的原子百分比为5～50at％，余量为X，其特征在于铂在合金表面的原子百分比为10～80at％，余量为X，条件是铂在合金表面的at％比铂在本体合金中的at％大至少25％。
适当地，铂在本体合金中的原子百分比为5～45at％，更适当地为5～35at％，更适当地为10～35at％，优选20～35at％。在一个实施方案中，铂在本体合金中的原子百分比为10～34at％。
适当地，铂在合金表面的原子百分比为20～60at％，更适当地为20～45at％，优选30～45at％。
适当地，铂在表面的原子百分比比铂在本体合金中的原子百分比大至少25％，更适当地大至少50％，最适当地大至少65％，并优选大至少75％(即，铂表面富集(the platinum surface enrichment))。适当地，铂表面富集为25％～500％，更适当地为50％～500％，最适当地为65％～500％并优选75％～500％。
铂表面富集是用以下公式来计算的：
在本发明上下文中，“at％”是指原子百分比，即以Pt和X总共的原子或摩尔数为基础Pt的百分数；不考虑任意另外的非金属组分(例如碳)。术语“合金”是指在Pt和X金属之间至少有某些密切混合，但是该密切混合在整个合金粒子中不必均匀。
可以通过本领域技术人员已知的标准程序，例如样品的湿化学分析消解(wet chemical analysis digestion)，接着用感应耦合等离子体(ICP)发射光谱法，来测定本体合金中Pt的原子百分比。Pt在表面的原子百分比可以通过X射线光电子能谱(XPS)或者高敏-低能离子散射(HS-LEIS)来测定。HS-LEIS是比XPS更为灵敏的表面技术，并且仅着眼于最外面的表面层；因此，尽管HS-LEIS和XPS都可以用来测定Pt在表面的原子百分比，但是表面富集百分比将稍有不同。
X适当地为选自贵金属(不同于铂)，即钌、铑、钯、铱、锇、金和银；或者过渡金属中的一种或多种金属。特别适当的金属包括Ru、Pd、Rh、Os、Sn、Bi、Pb、Ir、Mo、Sb、W、Au、Re，或其氧化物。更适当地，X为铑、铱、锇、钌或锡中的一种或多种。优选X为钌或锡，或者钌和锡。
由于合金催化剂的铂表面富集，本发明的催化剂显示出比预期更佳的催化活性，特别是当在燃料电池中用作电催化剂时。
本发明催化剂可以如下制备：一步连续沉积金属X，接着沉积铂，并随后在含有H2的气体中退火。退火步骤适合在高达500℃的温度下进行。
本发明催化剂可以在燃料电池中用作未负载催化剂(即作为金属黑)或用作负载催化剂(即分散在载体材料上)；优选本发明催化剂作为负载催化剂使用。适当地，PtX合金的量为基于负载催化剂总重量的5～90wt％，优选20～80wt％。在根据本发明的负载催化剂中，PtX合金适当地分散在导电载体材料，例如导电碳如油料炉黑、超导电炭黑(extra-conductive blacks)、乙炔黑及其石墨化形式中。示例性的碳包括Akzo Nobel Ketjen EC300J、Cabot Vulcan XC72R和Denka乙炔黑。本发明催化剂优选基本上由分散在导电碳材料上的PtX合金组成。
本发明的另一方面提供包含根据本发明催化剂的电极。催化剂可以未负载或者沉积在导电衬底上。可以使用熟知的技术，如EP 0 731 520中公开的那些，将催化剂沉积在衬底上。可以将催化剂配制成墨水，该墨水包含含水和/或有机溶剂，任选的聚合物粘合剂和任选的质子导电聚合物。使用诸如喷雾、印刷和刮刀方法等技术可以将墨水沉积到导电衬底上。典型的衬底包括基于炭纸(例如从日本Toray公司获得的纸，或者从日本Mitsubishi Rayon获得的U 105或U107纸)、纺织碳布(例如从日本Mitsubishi Chemicals获得的MK系列碳布)或者无纺碳纤维网(例如从美国E-TEK公司获得的ELAT系列无纺衬底；从德国Freudenberg FCCT KG获得的H2315系列；或者从德国SGLTechnologies GmbH获得的系列)的衬底。炭纸、布或者网通常用微粒材料进行改性，所述微粒材料嵌入层内或者涂覆在平面上，或者二者组合。微粒材料通常为炭黑和诸如聚四氟乙烯(PTFE)等聚合物的混合物。适当地，气体扩散衬底厚100～300μm。优选在与电催化层接触的气体扩散衬底面上存在诸如炭黑和PTFE等微粒材料层。
或者，其上施加本发明催化剂层的衬底可以是预形成气体扩散电极，或为阳极或为阴极，即已被施加催化剂层的气体扩散衬底(其可以如上所述)。
在聚合物电解质膜(PEM)燃料电池中，电解质为聚合物电解质膜。可以将电催化剂沉积到聚合物电解质膜的一面或两面上以形成催化膜。本发明另一方面提供沉积在聚合物电解质膜上的包含根据本发明催化剂的催化膜。可以使用众所周知的技术将催化剂沉积在膜上。可以将催化剂配制成墨水，或者直接沉积在膜上，或者沉积在空白贴花纸(decalblank)上从而随后转移到膜上。可以接着将一层或多层附加催化剂层(例如Pt，PtRu)施加到在膜上的本发明催化剂层上以形成具有两层或多层催化剂层的催化剂涂覆膜。所述一层或多层附加催化剂层可以是根据本发明的催化剂层，或者可以是通过常规技术，例如丝网印刷施加的常规催化剂层。
或者，其上施加本发明催化剂层的膜可以是预形成催化剂涂覆膜。此外，将获得多层结构，但是本发明催化剂层将是在膜上的最后一层，并因此最为接近气体扩散层。
膜可以是适用于燃料电池的任意膜，例如膜可以基于全氟化磺酸材料如(DuPont)，(Asahi Glass)和(Asahi Kasei)；这些膜可以未经改性而使用，或者可以，例如通过结合进添加剂，进行改性以改善高温性能。或者，膜可以基于磺化烃膜，例如获自Polyfuel，JSR，FuMaTech的那些和其他的。膜可以是包含质子导电材料和赋予诸如机械强度等性质的其他材料的复合膜。例如，如EP 0875524中所述，膜可以包含质子导电膜和石英纤维基质，或者膜可以包含膨胀型PTFE衬底。或者，膜可以基于掺杂了磷酸的聚苯并咪唑，而且包括来自开发商如PEMEAS的膜，例如将在120℃～180℃工作的膜，和其他新近开发的膜如膜。本发明催化剂层也适合与使用不同于质子的电荷载流子的膜，例如诸如从获自Solvay，FuMaTech的那些OH-导电膜，一起使用。
在本发明另一实施方案中，其上施加本发明催化剂的衬底是转移衬底(transfer substrate)。因此，本发明的另一方面提供包含本发明催化剂的转移衬底。转移衬底可以是本领域技术人员已知的任意适当的转移衬底，但是优选为聚合物材料，如聚四氟乙烯(PTFE)或聚丙烯(尤其是双轴取向聚丙烯，BOPP)或者聚合物涂布纸如聚氨酯涂布纸。转移衬底还可以是有机硅涂布纸(silicone release paper)或诸如铝箔等金属箔。然后可以通过本领域技术人员已知的技术，将本发明催化剂转移到气体扩散衬底、气体扩散电极、膜或者催化剂涂覆膜上。
在PEM燃料电池中，聚合物电解质膜插在两层催化剂层之间，而且各催化剂层与导电衬底接触。该五层组件被称作膜电极组件。本发明另一实施方案提供包含本发明催化剂层的膜电极组件(MEA)。MEA可以以多种方式来制备，包括但不限于：
(i)可以将离子导电膜夹在两个气体扩散电极(一个阳极和一个阴极)之间，至少其一为根据本发明的电极；
(ii)可以将仅在一面上涂覆了催化剂层的催化剂涂覆膜夹在：(i)气体扩散衬底和气体扩散电极之间，所述气体扩散衬底与膜的涂覆了催化剂层的那一面接触，或者(ii)两个气体扩散电极之间，并且其中催化剂层和气体扩散电极(一个或多个)中至少之一是根据本发明的；
(iii)可以将两个面都涂覆了催化剂层的催化剂涂覆膜夹在：(i)两个气体扩散衬底之间，(ii)气体扩散衬底和气体扩散电极之间或者(iii)两个气体扩散电极之间，并且其中催化剂层和气体扩散电极(一个或多个)中至少之一是根据本发明的。
MEA还可以包含密封和/或加强MEA边缘部分的组分，例如如WO2005/020356所述。通过本领域技术人员已知的常规方法组装MEA。
MEA可以用于燃料电池堆中，例如质子交换膜燃料电池(PEMFC)、直接甲醇燃料电池(DMFC)、高温燃料电池(在100℃～250℃的温度使用)或者碱性燃料电池。因此，本发明另一方面提供包含本发明MEA的燃料电池。可以使用常规方法将MEA结合进燃料电池中。
或者，本发明电极可以直接用于燃料电池，例如磷酸燃料电池中，其中电解质为在载体基质例如碳化硅中的液体磷酸。因此，本发明的另一方面提供燃料电池，特别是磷酸燃料电池，其包含本发明的电极。这样的燃料电池可以在150℃～210℃下工作。
本发明还提供结合了根据本发明的燃料电池的便携式设备(例如，便携式电源、便携式计算机或者移动电话)。
现在将参考下面的附图，进一步对本发明进行说明，所述附图是说明性的，并不限制本发明。
对比例1
获得市售PtRu催化剂(来自Johnson Matthey的12100)。
测定(本体粒子的重量％)50％Pt，25％Ru(本体中50at％的铂)
铂的表面原子百分比＝61∶39％(XPS)；46％(HS-LEIS)
与本体相比表面Pt富集＝22％(XPS)；没有表面富集(HS-LEIS)。
实施例1
使用Silverson混合器将Ketjen EC300J(1g)分散在水中。加入碳酸氢钠(8.41g)，搅拌碳浆料并加热至沸。沸腾30分钟后，加入Ru和Pt盐溶液并且另外持续沸腾1.5小时。[1g Pt作为H2PtCl6：4g，25％Pt，和2g Ru作为RuCl3：4.94g，40.47％Ru]。通过过滤回收催化剂并在滤床上清洗。将材料在105℃干燥过夜。在5％H2/N2中烧制干燥材料的样品。
收率(干燥，未还原的)＝5.06g
烧制条件：500℃，30分钟
烧制后从2g中得到1.57g
测定(本体粒子的重量％)25.7％Pt，44.8％Ru(本体中23at％的铂)
Pt的表面at％＝36.9％(XPS)
与本体相比表面Pt富集＝60％(XPS)
实施例2-7的一般方法
使用Silverson混合器将Ketjen EC300J(1g)分散在水(150ml)中。将浆料转移到装配了温度和pH探针以及与pH控制装置连接的两个进料管的烧杯中(如果需要，再加50ml水)。向水中加入Ru盐并将体积补足为100ml。将该溶液以10ml/min的速率与以可变速率的NaOH一起泵送到搅拌的碳浆料中以尽可能地维持pH为5.0～6.0(初始pH)。当加入完成后，任选将温度升至最高100℃，搅拌浆料并加入Pt盐。加入NaOH将pH维持在5.0～7.0(最终pH)。搅拌浆料。一旦反应结束，通过过滤回收催化剂并在滤床上清洗。将材料在105℃干燥过夜。在5％H2/N2中烧制干燥材料的样品。
实施例2
2g Ru作为RuCl3：4.94g，40.47％Ru
1g Pt作为硝酸铂：6.09g，16.41％Pt
NaOH：0.5M
pH(初始)5.0；pH(最终)5.0
收率(干燥，未还原的)＝5.04g
烧制条件：200℃，1小时
烧制后从2g样品得到1.55g
测定(本体粒子的重量％)21.5％Pt，44.7％Ru(本体中20at％的Pt)
Pt的表面原子百分比＝38.8％(XPS)
与本体相比表面Pt富集＝94％(XPS)
实施例3
2g Ru作为亚硝酰硝酸钌：15.37g，13.01％Ru
1g Pt作为硝酸铂：6.09g，16.41％Pt
NaOH：1.0M
pH(初始)6.0；pH(最终)7.0
收率(干燥，未还原的)＝5.48g
烧制条件：200℃，1小时
烧制后从2g样品得到1.4g
测定(本体粒子的重量％)22.7％Pt，44.4％Ru(本体中21at％的Pt)
Pt的表面原子百分比＝36.3％(XPS)
与本体相比表面Pt富集＝73％(XPS)
实施例4
2g Ru作为RuCl3：4.94g，40.47％Ru
1g Pt作为K2PtCl4：46.56％Pt
NaOH：0.5M(初次加入)和1.0M(第二次加入)
pH(初始)6.0；pH(最终)7.0
收率(干燥，未还原的)＝5.10g
烧制条件：200℃，1小时
烧制后从2g样品得到1.64g
测定(本体粒子的重量％)20.5％Pt，42.9％Ru(本体中21at％的Pt)
Pt的表面原子百分比＝39.6％(XPS)；37％(HS-LEIS)
与本体相比表面Pt富集＝89％(XPS)；76％(HS-LEIS)
实施例5
2g Ru作为RuCl3：4.94g，40.47％Ru
1g Pt作为硝酸铂：6.09g，16.41％Pt
NaOH：0.5M
pH(初始)5.0；pH(最终)5.0
收率(干燥，未还原的)＝5.04g
烧制条件：500℃，30分钟
烧制后从1.5g样品得到1.11g
测定(本体粒子的重量％)21.5％Pt，44.7％Ru(本体中20at％的Pt)
Pt的表面原子百分比＝38.8％(XPS)
与本体相比表面Pt富集＝94％(XPS)
实施例6
2.47g Ru作为RuCl3：6.19g，39.9％Ru
0.53g Pt作为K2PtCl4：1.13g 46.71％Pt
NaOH：0.5M(初次加入)和1.0M(第二次加入)
pH(初始)6.0；pH(最终)7.0
收率(干燥，未还原的)＝4.98g
烧制条件：200℃，30分钟
烧制后从2g样品得到1.55g
测定(本体粒子的重量％)12.7％Pt，54.0％Ru(本体中10at％的Pt)
Pt的表面原子百分比＝19％(HS-LEIS)
与本体相比表面Pt富集＝90％(HS-LEIS)
实施例7
1.64g Ru作为RuCl3：4.11g，39.9％Ru
1.36g Pt作为K2PtCl4：2.92g，46.55％Pt
NaOH：0.5M(初次加入)和1.0M(第二次加入)
pH(初始)6.0；pH(最终)7.0
收率(干燥，未还原的)＝5.07g
烧制条件：200℃，30分钟
测定(本体粒子的重量％)29.7％Pt，34.3％Ru(本体中30at％的Pt)
Pt的表面原子百分比＝50％(HS-LEIS)
与本体相比表面Pt富集＝67％(HS-LEIS)
实施例8：阳极极化数据
使用对比例1和实施例1-7所制备的催化剂来制备膜电极组件。使用EP 0731520所概述的技术将催化剂配制成墨水并且用来制备总金属负载量(Pt+Ru)为1.5mg/cm2的阳极电催化剂层。阴极电催化剂层包含标准Pt黑电催化剂。在直接甲醇试验电池中测试膜电极组件。图1-3示出包含实施例1-7和对比例1的电催化剂的膜电极组件在80℃的阳极半电池性能。即使本发明实施例包含显著少量的铂，含有本发明实施例的MEA的性能优于或者比得上对比例1的MEA性能。
Claims (12)
1.铂合金催化剂PtX，其中X为选自Ru、Rh、Os、Sn和Ir中的一种或多种金属，其中通过用样品的湿化学分析消解，接着用感应耦合等离子体(ICP)发射光谱法测得的铂在所述合金的本体中的原子百分比为5～35at％，余量为X，其特征在于通过X射线光电子能谱(XPS)或者高敏-低能离子散射(HS-LEIS)测得的铂在所述合金的表面的原子百分比为10～80at％，余量为X，条件是铂在所述合金的表面的at％比铂在所述合金的本体中的at％高至少25％。
2.根据权利要求1所述的铂合金催化剂PtX，其中X为钌或锡，或者钌和锡。
3.根据权利要求1-2中任意一项所述的铂合金催化剂PtX，其中所述催化剂未负载或者负载在分散载体材料上。
4.根据权利要求3所述的铂合金催化剂PtX，其中所述催化剂负载在分散载体材料上。
5.根据权利要求1所述的铂合金催化剂PtX，其中所述催化剂由分散在导电碳载体上的PtX合金组成。
6.包含根据权利要求1-5中任意一项所述的催化剂的电极。
7.包含根据权利要求1-5中任意一项所述的催化剂的催化膜。
8.包含根据权利要求1-5中任意一项所述的催化剂的转移衬底。
9.包含根据权利要求1-5中任意一项所述的催化剂的膜电极组件。
10.包含根据权利要求9所述的膜电极组件的燃料电池。
11.包含根据权利要求6所述的电极的燃料电池。
12.包含根据权利要求10或权利要求11所述的燃料电池的便携式设备。
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| CN107954879B (zh) * | 2017-12-07 | 2021-03-26 | 苏州大学 | 碳负载的钌纳米材料在制备n-烷基芳香胺化合物中的应用 |
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- 2008-07-22 US US12/670,000 patent/US8173324B2/en active Active
- 2008-07-22 DK DK08788586.9T patent/DK2170506T3/da active
- 2008-07-22 CN CN200880100306.7A patent/CN101808735B/zh not_active Expired - Fee Related
- 2008-07-22 JP JP2010517491A patent/JP5425771B2/ja active Active
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- 2008-07-22 EP EP08788586.9A patent/EP2170506B1/en active Active
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| EP0450849A2 (en) * | 1990-03-30 | 1991-10-09 | Johnson Matthey Public Limited Company | Catalyst material |
| CN1447468A (zh) * | 2003-04-29 | 2003-10-08 | 重庆大学 | 直接甲醇燃料电池甲醇氧化电极制备方法 |
| CN1962057A (zh) * | 2006-11-29 | 2007-05-16 | 山东大学 | 一种纳米多孔铂金合金催化剂及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| GB0714460D0 (en) | 2007-09-05 |
| US20100196789A1 (en) | 2010-08-05 |
| EP2170506A2 (en) | 2010-04-07 |
| KR20100047233A (ko) | 2010-05-07 |
| JP5425771B2 (ja) | 2014-02-26 |
| US8173324B2 (en) | 2012-05-08 |
| EP2170506B1 (en) | 2022-10-26 |
| KR101526028B1 (ko) | 2015-06-04 |
| CN101808735A (zh) | 2010-08-18 |
| WO2009013540A2 (en) | 2009-01-29 |
| WO2009013540A3 (en) | 2009-08-06 |
| JP2010534130A (ja) | 2010-11-04 |
| DK2170506T3 (da) | 2022-11-28 |
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