Cross Reference To Related Application

[0001] This application claims the benefit of U.S. Provisional Patent Application Number 62/652616, filed April 4, 2018, the disclosure of which is incorporated by reference herein in its entirety.

[0002] This invention was made with Government support under Contract No. DE-EE0007270 awarded by DOE. The Government has certain rights in this invention.

Background

[0003] Fuel cells produce electricity via electrochemical oxidation of a fuel and reduction of an oxidant. Fuel cells are generally classified by the type of electrolyte and the type of fuel and oxidant reactants. One type of fuel cell is a polymer electrolyte membrane fuel cell (PEMFC), where the electrolyte is a polymeric ion conductor and the reactants are hydrogen fuel and oxygen as the oxidant. The oxygen is often provided from the ambient air.

[0004] PEMFCs typically require the use of electrocatalysts to improve the reaction rate of the hydrogen oxidation reaction (HOR) and oxygen reduction reactions (ORR), which improve the PEMFC performance. PEMFC electrocatalysts often comprise platinum, a relatively expensive precious metal. It is typically desirable to minimize the platinum content in PEMFC increasing the catalyst activity per unit catalyst surface area (specific activity) and increasing the catalyst surface area per catalyst mass (specific surface area or specific area). The HOR and ORR occur on the catalyst surface, so increasing the specific surface area and/or the specific activity can reduce the devices to minimize cost. Sufficient platinum content, however, is needed to provide sufficient catalytic activity and PEMFC device performance. As such, there is a desire to increase the catalyst activity per unit catalyst mass (mass activity). There are two general approaches to increase the mass activity, namely amount of catalyst needed to achieve a desired absolute performance, reducing cost.

[0005] To maximize specific area, PEMFC electrocatalysts are often in the form of nanometer-scale thin films or particles on support materials. An exemplary support material for nanoparticle PEMFC electrocatalysts is carbon black, and an exemplary support material for thin film electrocatalysts is whiskers.

[0006] To increase the specific activity, PEMFC Pt ORR electrocatalysts often also comprise certain transition metals such as cobalt or nickel. Without being bound by theory, incorporation of certain transition metals into the Pt lattice is believed to induce contraction of the Pt atoms at the catalyst surface, which increases the kinetic reaction rate by modification of the molecular oxygen binding and dissociation energies and the binding energies of reaction intermediates and/or spectator species.

[0007] PEMFC electrocatalysts may incorporate other precious metals. For example, HOR PEMFC Pt electrocatalysts can be alloyed with ruthenium to improve tolerance to carbon monoxide, a known Pt catalyst poison. HOR and ORR PEMFC electrocatalysts may also incorporate iridium to facilitate improved activity for the oxygen evolution reaction (OER). Improved OER activity may improve the durability of the PEMFC under inadvertent operation in the absence of fuel and during PEMFC system startup and shutdown. Incorporation of iridium into the PEMFC ORR electrocatalyst, however, may result in decreased mass activity and higher catalyst cost. Iridium has relatively lower specific activity for ORR than platinum, potentially resulting in decreased mass activity. Iridium is also a precious metal, and thereby its incorporation can increase cost. PEMFC Pt electrocatalysts may also incorporate gold which is also a precious metal and can increase cost. Gold is known to be relatively inactive for HOR and ORR in acidic electrolytes. Incorporation of gold can result in substantial deactivation for HOR and ORR due to the propensity for gold to preferentially segregate to the electrocatalyst surface, blocking active catalytic sites.

[0008] PEMFC electrocatalysts may have different structural and compositional morphologies. The structural and compositional morphologies are often tailored through specific processing methods during the electrocatalyst fabrication, such as variations in the electrocatalyst deposition method and annealing methods. PEMFC electrocatalysts can be compositionally homogenous, compositionally layered, or may contain composition gradients throughout the electrocatalyst. Tailoring of composition profiles within the electrocatalyst may improve the activity and durability of electrocatalysts. PEMFC electrocatalyst particles or nanometer-scale films may have substantially smooth surfaces or have atomic or nanometer scale roughness. PEMFC electrocatalysts may be structurally homogenous or may be nanoporous, being comprised of nanometer-scale pores and solid catalyst ligaments.

[0009] As compared to structurally homogenous electrocatalysts, nanoporous PEMFC electrocatalysts may have higher specific area, thereby reducing cost. Nanoporous catalysts are comprised of numerous interconnected nanoscale catalyst ligaments, and the surface area of a nanoporous material depends upon the diameter and volumetric number density of the nanoscale ligaments. Surface area is expected to increase as the nanoscale ligaments diameter decreases and the volumetric number density increases. In PEMFC devices, electrocatalysts may lose performance over time due to a variety of degradation mechanisms, which induce structural and compositional changes. Such performance loss may shorten the practical lifetime of such systems. Electrocatalyst degradation may occur, for example, due to loss of electrocatalyst activity per unit surface area and loss of electrocatalyst surface area. Electrocatalyst specific activity may be lost, for example, due to the dissolution of electrocatalyst alloying elements. Nanoparticle and nano-scale thin film electrocatalysts may lose surface area, for example, due to Pt dissolution, particle sintering, and loss of surface roughness. Nanoporous electrocatalysts may additionally lose surface area, for example, due to increased nanoscale ligament diameter and decreased nanoscale ligament density.

[0010] Additional electrocatalysts and systems containing such catalysts are desired, including those that address one or more of the issues discussed above.

Summary

[0011] In one aspect, the present disclosure provides a catalyst comprising nanostructured elements comprising microstructured whiskers having an outer surface at least partially covered by a catalyst material comprising at least 90 (in some embodiments, at least 95, 96, 97, 98, 99, 99.5, 99.6, 99.7, 99.8, 99.9, or event 100) atomic percent collectively Pt, Ni, and Ru, wherein the Pt is present in a range from 33.9 to 35.9 atomic percent, the Ni is present in a range from 60.3 to 63.9 atomic percent, and the Ru is present in a range from 0.5 to 9.9 atomic percent (in some embodiments, the Pt is present in a range from 34.7 to 35.9 atomic percent, the Ni is present in a range from 61.8 to 63.9 atomic percent, and the Ru is present in a range from 0.5 to 5.9 atomic percent; the Pt is present in a range from 36.0 to 35.9 atomic percent, the Ni is present in a range from 61.0 to 63.9 atomic percent, and the Ru is present in a range from 0.5 to 5.2 atomic percent; the Pt is present in a range from 35.0 to 35.9 atomic percent, the Ni is present in a range from 62.2 to 63.9 atomic percent, and the Ru is present in a range from 0.5 to 4.9 atomic percent; the Pt is present in a range from 35.6 to 35.9 atomic percent, the Ni is present in a range from 63.3 to 63.9 atomic percent, and the Ru is present in a range from 0.5 to 2.0 atomic percent; the Pt is present in a range from 36.9 to 35.9 atomic percent, the Ni is present in a range from 62.5 to 63.9 atomic percent, and the Ru is present in a range from 0.5 to 1.0 atomic percent; the Pt is present in a range from 33.9 to 35.8 atomic percent, the Ni is present in a range from 60.3 to 63.7 atomic percent, and the Ru is present in a range from 1.0 to 9.9 atomic percent; the Pt is present in a range from 34.7 to 35.8 atomic percent, the Ni is present in a range from 61.8 to 63.7 atomic percent, and the Ru is present in a range from 1.0 to 5.9 atomic percent; the Pt is present in a range from 36.0 to 35.8 atomic percent, the Ni is present in a range from 61.0 to 63.7 atomic percent, and the Ru is present in a range from 1.0 to 5.2 atomic percent; the Pt is present in a range from 35.0 to 35.8 atomic percent, the Ni is present in a range from 62.2 to 63.7 atomic percent, and the Ru is present in a range from 1.0 to 4.9 atomic percent; the Pt is present in a range from 35.6 to 35.8 atomic percent, the Ni is present in a range from 63.3 to 63.7 atomic percent, and the Ru is present in a range from 1.0 to 2.0 atomic percent; the Pt is present in a range from 33.9 to 36.9 atomic percent, the Ni is present in a range from 60.3 to 62.5 atomic percent, and the Ru is present in a range from 1.0 to 9.9 atomic percent; the Pt is present in a range from 34.7 to 36.9 atomic percent, the Ni is present in a range from 61.8 to 62.5 atomic percent, and the Ru is present in a range from 1.0 to 5.9 atomic percent; the Pt is present in a range from 36.0 to 36.9 atomic percent, the Ni is present in a range from 61.0 to 62.5 atomic percent, and the Ru is present in a range from 1.0 to 5.2 atomic percent; the Pt is present in a range from 35.0 to 36.9 atomic percent, the Ni is present in a range from 62.2 to 62.5 atomic percent, and the Ru is present in a range from 1.0 to 4.9 atomic percent; the Pt is present in a range from 35.6 to 36.9 atomic percent, the Ni is present in a range from 63.3 to 62.5 atomic percent, and the Ru is present in a range from 1.0 to 2.0 atomic percent; the Pt is present in a range from 33.9 to 35.6 atomic percent, the Ni is present in a range from 60.3 to 63.3 atomic percent, and the Ru is present in a range from 2.0 to 9.9 atomic percent; the Pt is present in a range from 34.7 to 35.6 atomic percent, the Ni is present in a range from 61.8 to 63.3 atomic percent, and the Ru is present in a range from 2.0 to 5.9 atomic percent; the Pt is present in a range from 36.0 to 35.6 atomic percent, the Ni is present in a range from 61.0 to 63.3 atomic percent, and the Ru is present in a range from 2.0 to 5.2 atomic percent; and even the Pt is present in a range from 35.0 to 35.6 atomic percent, the Ni is present in a range from 62.2 to 63.3 atomic percent, and the Ru is present in a range from 2.0 to 4.9 atomic percent), and wherein the total atomic percent of Pt, Ni, and Ru equals 100.

[0011] In some embodiments, the catalyst material functions as an oxygen reduction catalyst material.

[0012] In some embodiments, catalysts described herein have been annealed.

[0013] Surprisingly, Applicants discovered the addition of ruthenium to PtNi catalyst can substantially improve retention of mass activity, specific area, and/or performance after accelerated electrocatalyst aging. Ruthenium was observed to improve the durability when incorporated at the surface of the catalyst prior to annealing.

[0014] Catalysts described herein are useful, for example, in fuel cell membrane electrode assemblies.

Brief Description of Drawings

[0015] FIG. 1 is a side view of an exemplary catalyst described herein.

[0016] FIG. 2 is a schematic of an exemplary fuel cell.

[0017] FIG. 3 is a plot of the electrocatalyst mass activity of Examples 1-9 and Comparative Examples A and B catalysts, normalized to platinum content.

[0018] FIG. 4 is a plot of the electrocatalyst surface area of Examples 1-9 and Comparative Examples A and B catalysts, normalized to platinum content.

[0019] FIG. 5 is a plot of the electrocatalyst specific activity of Examples 1-9 and Comparative Examples A and B catalysts, normalized to Pt surface area.

Detailed Description

[0020] Referring to FIG. 1, exemplary catalyst described herein 100 on substrate 108 has nanostructured elements 102 with microstructured whiskers 104 having outer surface 105 at least partially covered by catalyst material 106 comprising at least 90 atomic percent collectively Pt, Ni, and Ru, wherein the Pt is present in a range from 33.9 to 35.9 atomic percent, the Ni is present in a range from 60.3 to 63.9 atomic percent, and the Ru is present in a range from 0.5 to 9.9 atomic percent, and wherein the total atomic percent of Pt, Ni, and Ru equals 100.

[0021] Suitable whiskers can be provided by techniques known in the art, including those described in U.S. Pat. Nos. 4,812,352 (Debe), 5,039,561 (Debe), 5,338,430 (Parsonage et ah), 6,136,412 (Spiewak et ah), and 7,419,741 (Vemstrom et ah), the disclosures of which are incorporated herein by reference. In general, microstructured whiskers can be provided, for example, by vacuum depositing (e.g., by sublimation) a layer of organic or inorganic material onto a substrate (e.g., a microstructured catalyst transfer polymer sheet), and then, in the case of perylene red deposition, converting the perylene red pigment into microstructured whiskers by thermal annealing. Typically, the vacuum deposition steps are carried out at total pressures at or below about 10 ³ Torr or 0.1 Pascal. Exemplary microstructures are made by thermal sublimation and vacuum annealing of the organic pigment C.I. Pigment Red 149 (i.e., N,N'-di(3,5-xylyl)perylene-3,4:9,lO-bis(dicarboximide)). Methods for making organic microstructured layers are reported, for example, in Materials Science and Engineering, A158 (1992), pp. 1-6; J. Vac. Sci. Technol. A, 5, (4), July/August 1987, pp. 1914-16; J. Vac. Sci. Technol. A, 6, (3), May/August 1988, pp. 1907-11; Thin Solid Films, 186, 1990, pp. 327-47; J. Mat. Sci., 25, 1990, pp. 5257-68; Rapidly Quenched Metals, Proc. of the Fifth Int. Conf. on Rapidly Quenched Metals, Wurzburg, Germany (Sep. 3-7, 1984), S. Steeb et ah, eds., Elsevier Science Publishers B.V., New York, (1985), pp. 1117-24; Photo. Sci. and Eng., 24, (4), July/August 1980, pp. 211-16; and U.S. Pat. Nos. 4,340,276 (Maffitt et al.) and 4,568,598 (Bilkadi et al.), the disclosures of which are incorporated herein by reference. Properties of catalyst layers using carbon nanotube arrays are reported in the article“High Dispersion and Electrocatalytic Properties of Platinum on Well-Aligned Carbon Nanotube Arrays”, Carbon, 42, (2004), pp. 191-197. Properties of catalyst layers using grassy or bristled silicon are reported, for example, in U.S. Pat. App. Pub. No. 2004/0048466 Al (Gore et al.).

[0022] Vacuum deposition may be carried out in any suitable apparatus (see, e.g., U.S. Pat. Nos. 5,338,430 (Parsonage et al.), 5,879,827 (Debe et al.), 5,879,828 (Debe et al.), 6,040,077 (Debe et al.), and 6,319,293 (Debe et al.), and U.S. Pat. App. Pub. No. 2002/0004453 Al (Haugen et al.), the disclosures of which are incorporated herein by reference). One exemplary apparatus is depicted schematically in FIG. 4A of U.S. Pat. No. 5,338,430 (Parsonage et al.), and discussed in the accompanying text, wherein the substrate is mounted on a drum, which is then rotated over a sublimation or evaporation source for depositing the organic precursor (e.g., perylene red pigment) prior to annealing the organic precursor in order to form the whiskers.

[0023] Typically, the nominal thickness of deposited perylene red pigment is in a range from about 50 nm to 500 nm. Typically, the whiskers have an average cross-sectional dimension in a range from 20 nm to 60 nm, an average length in a range from 0.3 micrometer to 3 micrometers, and an areal number density in a range from 30 to 70 whiskers per square micrometer. [0024] In some embodiments, the whiskers are attached to a backing. Exemplary backings comprise polyimide, nylon, metal foils, or other materials that can withstand the thermal annealing temperature up to 300°C. In some embodiments, the backing has an average thickness in a range from 25 micrometers to 125 micrometers.

[0025] In some embodiments, the backing has a microstructure on at least one of its surfaces. In some embodiments, the microstructure is comprised of substantially uniformly shaped and sized features at least three (in some embodiments, at least four, five, ten, or more) times the average size of the whiskers. The shapes of the microstructures can, for example, be V-shaped grooves and peaks (see, e.g., U.S. Pat. No. 6,136,412 (Spiewak et ak), the disclosure of which is incorporated herein by reference) or pyramids (see, e.g., U.S. Pat. No. 7,901,829 (Debe et ak), the disclosure of which is incorporated herein by reference). In some embodiments, some fraction of the microstructure features extends above the average or majority of the microstructured peaks in a periodic fashion, such as every 3 I ^st V-groove peak being 25% or 50% or even 100% taller than those on either side of it. In some embodiments, this fraction of features that extends above the majority of the microstructured peaks can be up to 10% (in some embodiments up to 3%, 2%, or even up to 1%). Use of the occasional taller microstructure features may facilitate protecting the uniformly smaller microstructure peaks when the coated substrate moves over the surfaces of rollers in a roll-to-roll coating operation. The occasional taller feature touches the surface of the roller rather than the peaks of the smaller microstructures, so much less of the microstructured material or whisker material is likely to be scraped or otherwise disturbed as the substrate moves through the coating process. In some embodiments, the microstructure features are substantially smaller than half the thickness of the membrane that the catalyst will be transferred to in making a membrane electrode assembly. This is so that during the catalyst transfer process, the taller microstructure features do not penetrate through the membrane where they may overlap the electrode on the opposite side of the membrane. In some embodiments, the tallest microstructure features are less than l/3 ^rd or l/4 ^th of the membrane thickness. For the thinnest ion exchange membranes (e.g., about 10 micrometers to 15 micrometers in thickness), it may be desirable to have a substrate with microstructured features no larger than about 3 micrometers to 4.5 micrometers talk The steepness of the sides of the V-shaped or other microstructured features or the included angles between adjacent features may, in some embodiments, be desirable to be on the order of 90° for ease in catalyst transfer during a lamination-transfer process and to have a gain in surface area of the electrode that comes from the square root of two (1.414) surface area of the microstructured layer relative to the planar geometric surface of the substrate backing.

[0026] In general, the catalyst can be deposited by techniques known in the art. Exemplary deposition techniques include those independently selected from the group consisting of sputtering (including reactive sputtering), atomic layer deposition, molecular organic chemical vapor deposition, molecular beam epitaxy, thermal physical vapor deposition, vacuum deposition by electrospray ionization, and pulse laser deposition. Additional general details can be found, for example, in U.S. Pat. Nos. 5,879,827 (Debe et al.), 6,040,077 (Debe et al.), and 7,419,741 (Vemstrom et al.), the disclosures of which are incorporated herein by reference. The thermal physical vapor deposition method uses suitable elevated temperature (e.g., via resistive heating, electron beam gun, or laser) to melt or sublimate the target (source material) into a vapor state, which is in turn passed through a vacuum space, then condensing of the vaporized form onto substrate surfaces. Thermal physical vapor deposition equipment is known in the art, including that available, for example, as a metal evaporator or as an organic molecular evaporator from CreaPhys GmbH, Dresden, Germany, under the trade designations “METAL EVAPORATOR (ME-SERIES)” or “ORGANIC MOLECULAR EVAPORATOR (DE- SERIES)” respectively; another example of an organic materials evaporator is available from Mantis Deposition LTD, Oxfordshire, UK, under the trade designation “ORGANIC MATERIALS EVAPORATIOR (ORMA-SERIES) .” Catalyst material comprising multiple alternating layers can be sputtered, for example, from multiple targets (e.g., Pt is sputtered from a first target, Ni is sputtered from a second target, and Ru from a third, or from a target(s) comprising more than one element (e.g., Pt and Ni)). If the catalyst coating is done with a single target, it may be desirable that the coating layer be applied in a single step onto the gas distribution layer, gas dispersion layer, catalyst transfer layer, or membrane, so that the heat of condensation of the catalyst coating heats the underlying catalyst or support Pt, Ni, or Ru atoms as applicable and substrate surface sufficient to provide enough surface mobility that the atoms are well mixed and form thermodynamically stable alloy domains. Alternatively, for example, the substrate can also be provided hot or heated to facilitate this atomic mobility. In some embodiments, sputtering is conducted at least in part in an atmosphere comprising argon. Organometallic forms of catalysts can be deposited, for example, by soft or reactive landing of mass selected ions. Soft landing of mass-selected ions is used to transfer catalytically-active metal complexes complete with organic ligands from the gas phase onto an inert surface. This method can be used to prepare materials with defined active sites and thus achieve molecular design of surfaces in a highly controlled way under either ambient or traditional vacuum conditions. For additional details see, for example, Johnson et al., Anal. Chem., 2010, 82, pp. 5718-5727, and Johnson et al., Chemistry: A European Journal, 2010, 16, pp. 14433-14438, the disclosures of which are incorporated herein by reference.

[0027] The planar equivalent thickness of an individual deposited catalyst layer is the thickness if deposited on a substantially flat, planar substrate. The planar equivalent thickness may depend, for example, on the areal catalyst loading of the layer and the catalyst density. For example, the planar equivalent thickness of a single layer of Pt with 10 micrograms of Pt per cm ² planar area and density of 21.45 g/cm ³ deposited is calculated as 4.7 nm, and the thickness of a Ni layer (8.90 g/cm ³ ) with the same areal loading is 11.2 nm. The thickness of a deposited layer can range from a sub-monolayer to several monolayers in thickness. A monolayer is a single, closely packed layer of atoms or molecules. The thickness of a monolayer is of the dimension of the atomic or molecular diameter. The diameter of a Pt atom is about 0.27 nm. The diameter of a Ni atom is about 0.27 nm. The diameter of a Ru atom is about 0.26 nm. A sub-monolayer is the same physical thickness of a monolayer, but contains fewer atoms or molecules than a closely packed layer. For example, a Pt sub-monolayer which had 50% of the number of Pt atoms per unit area as a full monolayer has a calculated thickness which is 50% of a full monolayer (i.e., about 0.135 nm). One or more layers can be deposited, resulting in a catalyst material with an overall planar equivalent thickness equal to the sum of each constituent layer’s planar equivalent thickness.

[0028] In some embodiments, the catalyst material has a thickness that is the planar equivalent thickness of the catalyst material divided by the combined surface area of the whiskers and the backing. For example, a catalyst material with a planar equivalent thickness of 20 nm deposited onto a surface comprising microstructured whiskers on a planar backing with a combined surface area of 10 cm ² of surface area per cm ² of planar backing area will result in a catalyst thickness of 2 nm on the whisker. The surface area of the whiskers depends upon the whisker cross-sectional dimension, whisker length, and whisker areal number density (number of whiskers per unit area of backing). In some embodiments, the surface area of the whiskers is in a range from 1 to 100 cm ² per cm ² of backing surface area (in some embodiments, in a range from 2 to 50 cm ² per cm ² , 5 to 25 cm ² per cm ² , or even 5 to 15 cm ² per cm ² ). In some embodiments, the backing may have a surface area in a range of 1 to 10 cm ² per cm ² planar backing area (in some embodiments, in a range from 1 to 5 cm ² per cm ² , or even in a range from 1 to 2 cm ² per cm ² ). The combined surface area of the whiskers and the backing is the product of the whisker surface area and the backing surface area. For example, whiskers which have a surface area of 10 cm ² per cm ² backing area on a backing which has a surface area of 1.5 cm ² of surface area per cm ² planar backing area, will yield a combined surface area of 15 cm ² of combined surface area per cm ² planar backing area.

[0029] In some embodiments, methods for making catalyst material herein comprise annealing the catalyst. In general, annealing can be done by techniques known in the art, including heating the catalyst material via, for example, in an oven or furnace, with a laser, and with infrared techniques. Annealing can be conducted, for example, in inert or reactive gas environments. Although not wanting to be bound by theory, it is believed annealing can induce structural changes on the atomic scale which can influence activity and durability of catalysts. Further, it is believed annealing nanoscale particles and fdms can induce mobility in the atomic constituent(s), which can cause growth of particles or thin fdm grains. In the case of multi-element mixtures, alloys, or layered particles and fdms, it is believed annealing can induce, for example, segregation of components within the particle or fdm to the surface, formation of random, disordered alloys, and formation of ordered intermetallics, depending upon the component element properties and the annealing environment. For additional details regarding annealing see, for example, van der Vliet et ah, Nature Materials, 2012, 11, pp. 1051-1058; Wang et ak, Nature Materials, 2013, 12, pp. 81-87, and U.S. Pat. No. 8,748,330 B2 (Debe et ak), the disclosures of which are incorporated herein by reference.

[0030] In some embodiments, the catalyst material comprises a layer comprising platinum and nickel and a layer comprising ruthenium on the layer comprising platinum and nickel. In some embodiments, the layer(s) comprising platinum and nickel collectively has a planar equivalent thickness up to 600 nm (in some embodiments, up to 575 nm, 550 nm, 500 nm, 400 nm, 300 nm, 200 nm, 100 nm, 75 nm, 50 nm, 25 nm, 10 nm, 5 nm, 2.5 nm, 1 nm, or even up to two monolayers (e.g., 0.4 nm); in some embodiments, in a range from 0.4 nm to 600 nm, 0.4 nm to 500 nm, 1 nm to 500 nm, 5 nm to 500 nm, 10 nm to 500 nm, 10 nm to 400 nm, or even 40 nm to 300 nm) and the layer comprising ruthenium has a planar equivalent thickness up to 100 nm (in some embodiments, up to 75 nm, 50 nm, 45 nm, 40 nm, 35 nm, 30 nm, 25 nm, 20 nm, 15 nm, 10 nm, 5 nm, 4 nm, 3 nm, 2 nm, 1 nm, a monolayer (e.g., 0.2 nm) or even less than a monolayer (e.g., 0.01 nm); in some embodiments, in a range from 0.01 nm to 100 nm, 1 nm to 50 nm, 5 nm to 40 nm, or even 5 nm to 35 nm). In some embodiments, each layer independently has a planar equivalent thickness up to 100 nm (in some embodiments, up to 50 nm, 20 nm, 15 nm, 10 nm, 5 nm, 4 nm, 3 nm, 2 nm, 1 nm, a monolayer (e.g., 0.2 nm), or even up to less than a monolayer (e.g. 0.01 nm); in some embodiments, in a range from 0.01 nm to 100 nm, 0.01 nm to 50 nm, 0.1 nm to 15 nm, 0.1 nm to 10 nm, or even 1 nm to 5 nm).

[0031] In some embodiments, the catalyst material comprises alternating layers comprising platinum and nickel and layers comprising ruthenium (i.e., a layer comprising platinum and nickel, a layer comprising ruthenium, a layer comprising platinum and nickel, a layer comprising ruthenium, etc.). In some embodiments, at least 2, 3, 4, 5, 10, 15, 20, 25, 50, 75, 100, 150, 200, 250, or even at least 275 sets of the alternating layers. In some embodiments, each layer independently has a planar equivalent thickness up to 100 nm (in some embodiments, up to 50 nm, 20 nm, 15 nm, 10 nm, 5 nm, 4 nm, 3 nm, 2 nm, 1 nm, a monolayer (e.g., 0.2 nm), or even up to less than a monolayer (e.g. 0.01 nm); in some embodiments, in a range from 0.01 nm to 100 nm, 0.01 nm to 50 nm, 0.1 nm to 15 nm, 0.1 nm to 10 nm, or even 1 nm to 5 nm).

[0032] In some embodiments, the catalyst material comprises a layer comprising platinum, a layer comprising nickel on the layer comprising platinum, and a layer comprising ruthenium on the layer comprising nickel. In some embodiments, the catalyst material comprises a layer comprising nickel, a layer comprising platinum on the layer comprising nickel, and a layer comprising ruthenium on the layer comprising platinum. In some embodiments, the catalyst has an exposed ruthenium surface layer (in some embodiments, the exposed ruthenium surface layer is a sub-monolayer of ruthenium).

[0033] In some embodiments, the catalyst material comprises repeating sequential individual layers of platinum, nickel, and ruthenium. In some embodiments, at least 2, 3, 4, 5, 10, 15, 20, 25, 50, 75, 100, 150, 200, 250, or even at least 275 sets of the repeating layers.

[0034] In some embodiments, the weight ratio of platinum to ruthenium is in a range from 6: 1 to 140: 1 (in some embodiments, in a range from 11 : 1 to 140: 1, 13: 1 to 140: 1, 13: 1 to 140: 1, 34: 1 to 140: 1, 69: 1 to 140: 1, 6: 1 to 70: 1, 11 : 1 to 70: 1, 13: 1 to 70: 1, 34: 1 to 70: 1, 6: 1 to 69: 1, 11 : 1 to 69: 1, 13: 1 to 69: 1, 34: 1 to 69: 1, 6: 1 to 34: 1, 11 : 1 to 34: 1, and even 13: 1 to 34: 1). In some embodiments, the atomic ratio of platinum to nickel is in a range from 32.5:67.5 to 90.0: 10.0 (in some embodiments, in a range from 32.5:67.5 to 80.0:20.0; 32.5:67.5 to 70.0:30.0; 32.5:67.5 to 60.0:40.0; 32.5:67.5 to 50.0:50.0; 32.5:67.5 to 42.5:57.5; 32.5:67.5 to 40.0:60.0; 32.5:67.5 to 37.5:62.5; 32.5:67.5 to 35.0:65.0; and even 35.0:65.0 to 40.0:60.0).

[0035] In some embodiments, the catalyst is essentially nonporous (i.e., the catalyst contains spherical and/or aspherical void volume, wherein the void volume is at least 75% contained within the catalyst thin film (in some embodiments, 85, 90, 95, 99, or even 100% contained within the catalyst thin film), and wherein the average diameter of the void volume is less than 1 nm (in some embodiments, less than 0.8 nm, 0.6 nm, 0.4 nm, 0.2 nm, or even 0.01 nm)).

[0036] In some embodiments, the thickness of the catalyst material on the whiskers can be up to 100 nm (in some embodiments, up to 50 nm, 20 nm, 15 nm, 10 nm, 5 nm, 4 nm, 3 nm, 2 nm, 1 nm, a monolayer (e.g., 0.2 nm), or even up to less than a monolayer (e.g. 0.01 nm); in some embodiments, in a range from 0.01 nm to 100 nm, 0.01 nm to 50 nm, 0.1 nm to 15 nm, 0.1 nm to 10 nm, 0.1 nm to 5 nm, or even 1 nm to 5 nm).

[0037] In some embodiments, methods for making catalyst described herein comprise annealing the catalyst.

[0038] In some embodiments, methods for making catalyst described herein comprise depositing platinum and nickel from a target comprising platinum and nickel and depositing ruthenium from a target comprising ruthenium. In some embodiments, methods for making catalyst described herein comprise depositing platinum and nickel from a PfsxNb target. In some embodiments, methods for making catalyst described herein comprise depositing layer(s) comprising platinum and nickel which each independently have a planar equivalent thickness in a range from 0.2 nm to 100 nm (in some embodiments, in a range from 0.2 nm to 20 nm, or even 0.2 nm to 10 nm) and the layer(s) comprising ruthenium each independently have a planar equivalent thickness in a range from 0.01 nm to 20 nm (in some embodiments, in a range from 0.01 nm to 10 nm, 0.01 nm to 5 nm, 0.02 nm to 5 nm, 0.02 nm to 1 nm, or even 0.1 nm to 1 nm).

[0039] In some embodiments, methods for making catalyst described herein comprise depositing platinum from a target comprising platinum, depositing nickel from a target comprising nickel, and depositing ruthenium from a target comprising ruthenium. In some embodiments, methods for making catalyst described herein comprise depositing a layer comprising platinum, an adjacent layer comprising nickel, and an adjacent layer comprising ruthenium collectively having a planar equivalent thickness in a range from 0.4 nm to 100 nm (in some embodiments, in a range from 1 nm to 100 nm, in a range from 1 nm to 50 nm, in a range from 1 nm to 30 nm, in a range from 2 nm to 50 nm, in a range from 2 nm to 30 nm, in a range from 5 nm to 50 nm, and even in a range from 10 nm to 30 nm). In some embodiments, methods for making catalyst described herein comprise depositing layer(s) comprising platinum each independently have a planar equivalent thickness in a range from 0.2 nm to 50 nm (in some embodiments, in a range from 0.2 nm to 20 nm, or even 0.2 nm to 10 nm), layers comprising nickel each independently have a planar equivalent thickness in a range from 0.2 nm to 100 nm (in some embodiments, in a range from 0.2 nm to 25 nm, or even 0.2 nm to 10 nm) and layer(s) comprising ruthenium each independently have a planar equivalent thickness in a range from 0.01 nm to 20 nm (in some embodiments, in a range from 0.01 nm to 10 nm, 0.01 nm to 5 nm, 0.02 nm to 5 nm, 0.02 nm to 1 nm, or even 0.1 nm to 1 nm).

[0040] In some embodiments, catalysts described herein may further comprise Cr or Ta. The Cr and/or Ta can be incorporated into the catalyst, for example, by modifying the methods described here in to use a target comprising Cr and/or Ta, as applicable.

[0041] Catalysts described herein are useful, for example, in fuel cell membrane electrode assemblies (MEAs). “Membrane electrode assembly” refers to a layered sandwich of fuel cell materials comprising a membrane, anode and cathode electrode layers, and gas diffusion layers. Typically, the cathode catalyst layer comprises a catalyst described herein, although in some embodiments, the anode catalyst layer independently comprises a catalyst described herein.

[0042] An MEA comprises, in order:

a first gas distribution layer having first and second opposed major surfaces;

an anode catalyst layer having first and second opposed major surfaces, the anode catalyst comprising a first catalyst;

an electrolyte membrane;

a cathode catalyst layer having first and second opposed major surfaces, the cathode catalyst comprising a second catalyst; and

a second gas distribution layer having first and second opposed major surfaces.

[0043] Electrolyte membranes conduct reaction intermediate ions between the anode and cathode catalyst layers. Electrolyte membranes preferably have high durability in the electrochemical environment, including chemical and electrochemical oxidative stability. Electrolyte membranes preferably have low ionic resistance for the transport of the reaction intermediate ions, but are relatively impermeable barriers for other ions, electrons, and reactant species. In some embodiments, the electrolyte membrane is a proton exchange membrane (PEM), which conducts cations. In PEM fuel cells, the electrolyte membrane preferably conducts protons. PEMs are typically a partially fluorinated or perfluorinated polymer comprised of a structural backbone and pendant cation exchange groups, PEMs are available, for example, from E. I. du Pont de Nemours and Company, Wilmington, DE, under the trade designation“NAFION;” Solvay, Brussels, Belgium, under the trade designation“AQUIVION;” 3M Company, St. Paul, MN, under the designation “3M PFSA MEMBRANE;” and Asahi Glass Co., Tokyo, Japan, under the trade designation“FLEMION.”

[0044] A gas distribution layer generally delivers gas evenly to the electrodes and, in some embodiments, conducts electricity. It also provides for removal of water in either vapor or liquid form, in the case of a fuel cell. Gas distribution layers are typically porous to allow reactant and product transport between the electrodes and the flow field. Sources of gas distribution layers include carbon fibers randomly oriented to form porous layers, in the form of non- woven paper or woven fabrics. The non-woven carbon papers are available, for example, from Mitsubishi Rayon Co., Ltd., Tokyo, Japan, under the trade designation “GRAFIL U-105;” Toray Corp., Tokyo, Japan, under the trade designation“TORAY;” AvCarb Material Solutions, Lowell, MA, under the trade designation“AVCARB;” SGL Group, the Carbon Company, Wiesbaden, Germany, under the trade designation“SIGRACET;” Freudenberg FCCT SE & Co. KG, Fuel Cell Component Technologies, Weinheim, Germany, under the trade designation“FREUDENBERG;” and Engineered Fibers Technology (EFT), Shelton, CT, under the trade designation“SPECTRACARB GDL.” The woven carbon fabrics or cloths are available, for example, from ElectroChem Inc., Wobum, MA, under the trade designations“EC-CC1-060” and“EC-AC-CLOTH;” NuVant Systems Inc., Crown Point, IN, under the trade designations“ELAT-LT” and“ELAT;” BASF Fuel Cell GmbH, North America, under the trade designation“E-TEK ELAT LT;” and Zoltek Corp., St. Louis, MO, under the trade designation“ZOLTEK CARBON CLOTH.” The non-woven paper or woven fabrics can be treated to modify its hydrophobicity (e.g., treatment with a polytetrafluoroethylene (PTFE) suspension with subsequent drying and annealing). Gas dispersion layers often comprise a porous layer of sub-micrometer electronically-conductive particles (e.g., carbon), and a binder (e.g., PTFE). Although not wanting to be bound by theory, it is believed that gas dispersion layers facilitate reactant and product water transport between the electrode and the gas distribution layers.

[0045] At least one of the anode or cathode catalyst is catalyst described herein (i.e., catalyst comprising nanostructured elements comprising microstructured whiskers having an outer surface at least partially covered by a catalyst material comprising at least 90 (in some embodiments, at least 95, 96, 97, 98, 99, 99.5, 99.6, 99.7, 99.8, 99.9, or event 100) atomic percent collectively Pt, Ni, and Ru, wherein the Pt is present in a range from 33.9 to 35.9 atomic percent, the Ni is present in a range from 60.3 to 63.9 atomic percent, and the Ru is present in a range from 0.5 to 9.9 atomic percent (in some embodiments, the Pt is present in a range from 34.7 to 35.9 atomic percent, the Ni is present in a range from 61.8 to 63.9 atomic percent, and the Ru is present in a range from 0.5 to 5.9 atomic percent; the Pt is present in a range from 36.0 to 35.9 atomic percent, the Ni is present in a range from 61.0 to 63.9 atomic percent, and the Ru is present in a range from 0.5 to 5.2 atomic percent; the Pt is present in a range from 35.0 to 35.9 atomic percent, the Ni is present in a range from 62.2 to 63.9 atomic percent, and the Ru is present in a range from 0.5 to 4.9 atomic percent; the Pt is present in a range from 35.6 to 35.9 atomic percent, the Ni is present in a range from 63.3 to 63.9 atomic percent, and the Ru is present in a range from 0.5 to 2.0 atomic percent; the Pt is present in a range from 36.9 to 35.9 atomic percent, the Ni is present in a range from 62.5 to 63.9 atomic percent, and the Ru is present in a range from 0.5 to 1.0 atomic percent; the Pt is present in a range from 33.9 to 35.8 atomic percent, the Ni is present in a range from 60.3 to 63.7 atomic percent, and the Ru is present in a range from 1.0 to 9.9 atomic percent; the Pt is present in a range from 34.7 to 35.8 atomic percent, the Ni is present in a range from 61.8 to 63.7 atomic percent, and the Ru is present in a range from 1.0 to 5.9 atomic percent; the Pt is present in a range from 36.0 to 35.8 atomic percent, the Ni is present in a range from 61.0 to 63.7 atomic percent, and the Ru is present in a range from 1.0 to 5.2 atomic percent; the Pt is present in a range from 35.0 to 35.8 atomic percent, the Ni is present in a range from 62.2 to 63.7 atomic percent, and the Ru is present in a range from 1.0 to 4.9 atomic percent; the Pt is present in a range from 35.6 to 35.8 atomic percent, the Ni is present in a range from 63.3 to 63.7 atomic percent, and the Ru is present in a range from 1.0 to 2.0 atomic percent; the Pt is present in a range from 33.9 to 36.9 atomic percent, the Ni is present in a range from 60.3 to 62.5 atomic percent, and the Ru is present in a range from 1.0 to 9.9 atomic percent; the Pt is present in a range from 34.7 to 36.9 atomic percent, the Ni is present in a range from 61.8 to 62.5 atomic percent, and the Ru is present in a range from 1.0 to 5.9 atomic percent; the Pt is present in a range from 36.0 to 36.9 atomic percent, the Ni is present in a range from 61.0 to 62.5 atomic percent, and the Ru is present in a range from 1.0 to 5.2 atomic percent; the Pt is present in a range from 35.0 to 36.9 atomic percent, the Ni is present in a range from 62.2 to 62.5 atomic percent, and the Ru is present in a range from 1.0 to 4.9 atomic percent; the Pt is present in a range from 35.6 to 36.9 atomic percent, the Ni is present in a range from 63.3 to 62.5 atomic percent, and the Ru is present in a range from 1.0 to 2.0 atomic percent; the Pt is present in a range from 33.9 to 35.6 atomic percent, the Ni is present in a range from 60.3 to 63.3 atomic percent, and the Ru is present in a range from 2.0 to 9.9 atomic percent; the Pt is present in a range from 34.7 to 35.6 atomic percent, the Ni is present in a range from 61.8 to 63.3 atomic percent, and the Ru is present in a range from 2.0 to 5.9 atomic percent; the Pt is present in a range from 36.0 to 35.6 atomic percent, the Ni is present in a range from 61.0 to 63.3 atomic percent, and the Ru is present in a range from 2.0 to 5.2 atomic percent; and even the Pt is present in a range from 35.0 to 35.6 atomic percent, the Ni is present in a range from 62.2 to 63.3 atomic percent, and the Ru is present in a range from 2.0 to 4.9 atomic percent), and wherein the total atomic percent of Pt, Ni, and Ru equals 100. The“other catalyst layer” can be a conventional catalyst known in the art, and provided by techniques known in the art (e.g., U.S. Pat. Nos. 5,759,944 (Buchanan et ah), 5,068,161 (Keck et ah), and 4,447,506 (Luczak et al.)), the disclosures of which are incorporated herein by reference.

[0046] A fuel cell is an electrochemical device that combines hydrogen fuel and oxygen from the air to produce electricity, heat, and water. Fuel cells do not utilize combustion, and as such, fuel cells produce little if any hazardous effluents. Fuel cells convert hydrogen fuel and oxygen directly into electricity, and can be operated at much higher efficiencies than internal combustion electric generators, for example.

[0047] Referring to FIG. 2, exemplary fuel cell 200 includes first gas distribution layer 201 adjacent to anode 203. Adjacent anode 203 is an electrolyte membrane 204. Cathode 205 is situated adjacent the electrolyte membrane 204, and second gas distribution layer 207 is situated adjacent cathode 205. In operation, hydrogen fuel is introduced into the anode portion of the fuel cell 200, passing through the first gas distribution layer 201 and over anode 203. At anode 203, the hydrogen fuel is separated into hydrogen ions (H ⁺ ) and electrons (e ).

[0048] Electrolyte membrane 204 permits only the hydrogen ions or protons to pass through electrolyte membrane 204 to the cathode portion of fuel cell 200. The electrons cannot pass through the electrolyte membrane 204 and, instead, flow through an external electrical circuit in the form of electric current. This current can power an electric load 217, such as an electric motor, or be directed to an energy storage device, such as a rechargeable battery.

[0049] Oxygen flows into the cathode side of fuel cell 200 via second distribution layer 207. As the oxygen passes over cathode 205, oxygen, protons, and electrons combine to produce water and heat.

Exemplary Embodiments

1A. A catalyst comprising nanostructured elements comprising microstructured whiskers having an outer surface at least partially covered by a catalyst material comprising at least 90 (in some embodiments, at least 95, 96, 97, 98, 99, 99.5, 99.6, 99.7, 99.8, 99.9, or event 100) atomic percent collectively Pt, Ni, and Ru, wherein the Pt is present in a range from 33.9 to 35.9 atomic percent, the Ni is present in a range from 60.3 to 63.9 atomic percent, and the Ru is present in a range from 0.5 to 9.9 atomic percent (in some embodiments, the Pt is present in a range from 34.7 to 35.9 atomic percent, the Ni is present in a range from 61.8 to 63.9 atomic percent, and the Ru is present in a range from 0.5 to 5.9 atomic percent; the Pt is present in a range from 36.0 to 35.9 atomic percent, the Ni is present in a range from 61.0 to 63.9 atomic percent, and the Ru is present in a range from 0.5 to 5.2 atomic percent; the Pt is present in a range from 35.0 to 35.9 atomic percent, the Ni is present in a range from 62.2 to 63.9 atomic percent, and the Ru is present in a range from 0.5 to 4.9 atomic percent; the Pt is present in a range from 35.6 to 35.9 atomic percent, the Ni is present in a range from 63.3 to 63.9 atomic percent, and the Ru is present in a range from 0.5 to 2.0 atomic percent; the Pt is present in a range from 36.9 to 35.9 atomic percent, the Ni is present in a range from 62.5 to 63.9 atomic percent, and the Ru is present in a range from 0.5 to 1.0 atomic percent; the Pt is present in a range from 33.9 to 35.8 atomic percent, the Ni is present in a range from 60.3 to 63.7 atomic percent, and the Ru is present in a range from 1.0 to 9.9 atomic percent; the Pt is present in a range from 34.7 to 35.8 atomic percent, the Ni is present in a range from 61.8 to 63.7 atomic percent, and the Ru is present in a range from 1.0 to 5.9 atomic percent; the Pt is present in a range from 36.0 to 35.8 atomic percent, the Ni is present in a range from 61.0 to 63.7 atomic percent, and the Ru is present in a range from 1.0 to 5.2 atomic percent; the Pt is present in a range from 35.0 to 35.8 atomic percent, the Ni is present in a range from 62.2 to 63.7 atomic percent, and the Ru is present in a range from 1.0 to 4.9 atomic percent; the Pt is present in a range from 35.6 to 35.8 atomic percent, the Ni is present in a range from 63.3 to 63.7 atomic percent, and the Ru is present in a range from 1.0 to 2.0 atomic percent; the Pt is present in a range from 33.9 to 36.9 atomic percent, the Ni is present in a range from 60.3 to 62.5 atomic percent, and the Ru is present in a range from 1.0 to 9.9 atomic percent; the Pt is present in a range from 34.7 to 36.9 atomic percent, the Ni is present in a range from 61.8 to 62.5 atomic percent, and the Ru is present in a range from 1.0 to 5.9 atomic percent; the Pt is present in a range from 36.0 to 36.9 atomic percent, the Ni is present in a range from 61.0 to 62.5 atomic percent, and the Ru is present in a range from 1.0 to 5.2 atomic percent; the Pt is present in a range from 35.0 to 36.9 atomic percent, the Ni is present in a range from 62.2 to 62.5 atomic percent, and the Ru is present in a range from 1.0 to 4.9 atomic percent; the Pt is present in a range from 35.6 to 36.9 atomic percent, the Ni is present in a range from 63.3 to 62.5 atomic percent, and the Ru is present in a range from 1.0 to 2.0 atomic percent; the Pt is present in a range from 33.9 to 35.6 atomic percent, the Ni is present in a range from 60.3 to 63.3 atomic percent, and the Ru is present in a range from 2.0 to 9.9 atomic percent; the Pt is present in a range from 34.7 to 35.6 atomic percent, the Ni is present in a range from 61.8 to 63.3 atomic percent, and the Ru is present in a range from 2.0 to 5.9 atomic percent; the Pt is present in a range from 36.0 to 35.6 atomic percent, the Ni is present in a range from 61.0 to 63.3 atomic percent, and the Ru is present in a range from 2.0 to 5.2 atomic percent; and even the Pt is present in a range from 35.0 to 35.6 atomic percent, the Ni is present in a range from 62.2 to 63.3 atomic percent, and the Ru is present in a range from 2.0 to 4.9 atomic percent), and wherein the total atomic percent of Pt, Ni, and Ru equals 100.

2A. The catalyst of Exemplary Embodiment 1A, wherein the catalyst material comprises a layer comprising platinum and nickel and a layer comprising ruthenium on the layer comprising platinum and nickel.

3A. The catalyst of Exemplary Embodiment 2A, wherein the layer(s) comprising platinum and nickel collectively has a planar equivalent thickness up to 600 nm (in some embodiments, up to 575 nm, 550 nm, 500 nm, 400 nm, 300 nm, 200 nm, 100 nm, 75 nm, 50 nm, 25 nm, 10 nm, 5 nm, 2.5 nm, 1 nm, or even up to two monolayers (e.g., 0.4 nm); in some embodiments, in a range from 0.4 nm to 600 nm, 0.4 nm to 500 nm, 1 nm to 500 nm, 5 nm to 500 nm, 10 nm to 500 nm, 10 nm to 400 nm, or even 40 nm to 300 nm) and the layer comprising ruthenium has a planar equivalent thickness up to 100 nm (in some embodiments, up to 75 nm, 50 nm, 45 nm, 40 nm, 35 nm, 30 nm, 25 nm, 20 nm, 15 nm, 10 nm, 5 nm, 4 nm, 3 nm, 2 nm, 1 nm, a monolayer (e.g., 0.2 nm) or even less than a monolayer (e.g., 0.01 nm); in some embodiments, in a range from 0.01 nm to 100 nm, 1 nm to 50 nm, 5 nm to 40 nm, or even 5 nm to 35 nm).

4A. The catalyst of Exemplary Embodiment 3A, wherein each layer independently has a planar equivalent thickness up to 100 nm (in some embodiments, up to 50 nm, 20 nm, 15 nm, 10 nm, 5 nm, 4 nm, 3 nm, 2 nm, 1 nm, a monolayer (e.g., 0.2 nm), or even up to less than a monolayer (e.g. 0.01 nm); in some embodiments, in a range from 0.01 nm to 100 nm, 0.01 nm to 50 nm, 0.1 nm to 15 nm, 0.1 nm to 10 nm, or even 1 nm to 5 nm).

5A. The catalyst of Exemplary Embodiment 1A, wherein the catalyst material comprises alternating layers comprising platinum and nickel and layers comprising ruthenium (i.e., a layer comprising platinum and nickel, a layer comprising ruthenium, a layer comprising platinum and nickel, a layer comprising ruthenium, etc.). In some embodiments, at least 2, 3, 4, 5, 10, 15, 20, 25, 50, 75, 100, 150, 200, 250, or even at least 275 sets of the alternating layers.

6A. The catalyst of Exemplary Embodiment 5A, wherein each layer independently has a planar equivalent thickness up to 100 nm (in some embodiments, up to 50 nm, 20 nm, 15 nm, 10 nm, 5 nm, 4 nm, 3 nm, 2 nm, 1 nm, a monolayer (e.g., 0.2 nm), or even up to less than a monolayer (e.g. 0.01 nm); in some embodiments, in a range from 0.01 nm to 100 nm, 0.01 nm to 50 nm, 0.1 nm to 15 nm, 0.1 nm to 10 nm, or even 1 nm to 5 nm).

7A. The catalyst of Exemplary Embodiment 1A, wherein the catalyst material comprises a layer comprising platinum, a layer comprising nickel on the layer comprising platinum, and a layer comprising ruthenium on the layer comprising nickel.

8A. The catalyst of Exemplary Embodiment 1A, wherein the catalyst material comprises a layer comprising nickel, a layer comprising platinum on the layer comprising nickel, and a layer comprising ruthenium on the layer comprising platinum.

9A. The catalyst of any preceding A Exemplary Embodiment having an exposed ruthenium surface layer (in some embodiments, the exposed ruthenium surface layer is a sub-monolayer of ruthenium).

10A. The catalyst of Exemplary Embodiment 1A, wherein the catalyst material comprises repeating sequential individual layers of platinum, nickel, and ruthenium. In some embodiments, at least 2, 3, 4, 5, 10, 15, 20, 25, 50, 75, 100, 150, 200, 250, or even at least 275 sets of the repeating layers.

11A. The catalyst of any preceding A Exemplary Embodiment, wherein the weight ratio of platinum to ruthenium is in a range from 6: 1 to 140: 1 (in some embodiments, in a range from 11 : 1 to 140: 1, in a range from 13: 1 to 140: 1, 13: 1 to 140: 1, 34: 1 to 140: 1, 69: 1 to 140: 1, 6: 1 to 70: 1, 11 : 1 to 70: 1, 13: 1 to 70: 1, 34: 1 to 70: 1, 6: 1 to 69: 1, 11 : 1 to 69: 1, 13: 1 to 69: 1, 34: 1 to 69: 1, 6: 1 to 34: 1, 11 : 1 to 34: 1, or even 13: 1 to 34: 1). 12A. The catalyst of any preceding A Exemplary Embodiment, wherein the atomic ratio of platinum to nickel is in a range from 32.5:67.5 to 90.0: 10.0 (in some embodiments, in a range from 32.5:67.5 to 80.0:20.0; 32.5:67.5 to 70.0:30.0; 32.5:67.5 to 60.0:40.0; 32.5:67.5 to 50.0:50.0; 32.5:67.5 to 42.5:57.5; 32.5:67.5 to 40.0:60.0; 32.5:67.5 to 37.5:62.5; 32.5:67.5 to 35.0:65.0; and even 35.0:65.0 to 40.0:60.0).

13 A. The catalyst of any preceding A Exemplary Embodiment, wherein the catalyst is essentially nonporous.

14A. The catalyst of any preceding A Exemplary Embodiment, wherein the catalyst material has a thickness up to 100 nm (in some embodiments, up to 50 nm, 20 nm, 15 nm, 10 nm, 5 nm, 4 nm, 3 nm, 2 nm, 1 nm, a monolayer (e.g., 0.2 nm), or even up to less than a monolayer (e.g. 0.01 nm); in some embodiments, in a range from 0.01 nm to 100 nm, 0.01 nm to 50 nm, 0.1 nm to 15 nm, 0.1 nm to 10 nm, 0.1 nm to 5 nm, or even 1 nm to 5 nm).

15 A. A fuel cell membrane electrode assembly comprising the catalyst of any preceding A Exemplary

Embodiment.

16A. The fuel cell membrane electrode assembly of Exemplary Embodiment 15 A, wherein the catalyst is an oxygen reduction reaction catalyst.

IB. A method comprising annealing the catalyst of any of Exemplary Embodiments 1 A to 14A.

IC. A method of making the catalyst of any of Exemplary Embodiments 1A to 14A, the method comprising depositing platinum and nickel from a target comprising platinum and nickel and depositing ruthenium from a target comprising ruthenium.

2C. The method of Exemplary Embodiment 1C, wherein the target is a PfsxNb target.

3C. The method of any preceding C Exemplary Embodiment, wherein layer(s) comprising platinum and nickel each independently have a planar equivalent thickness in a range from 0.2 nm to 100 nm (in some embodiments, in a range from 0.2 nm to 20 nm, or even 0.2 nm to 10 nm) and the layer(s) comprising ruthenium each independently have a planar equivalent thickness in a range from 0.01 nm to 20 nm (in some embodiments, in a range from 0.01 nm to 10 nm, 0.01 nm to 5 nm, 0.02 nm to 5 nm, 0.02 nm to 1 nm, or even 0.1 nm to 1 nm).

4C. The method of any of preceding C Exemplary Embodiment, further comprising annealing the catalyst.

1D. A method of making the catalyst of any of Exemplary Embodiments 1A to 14A, the method comprising depositing platinum from a target comprising platinum, depositing nickel from a target comprising nickel, and depositing ruthenium from a target comprising ruthenium.

2D. The method of Exemplary Embodiment 1D, wherein a layer comprising platinum, an adjacent layer comprising nickel, and an adjacent layer comprising ruthenium collectively having a planar equivalent thickness in a range from 0.4 nm to 100 nm (in some embodiments, in a range from 1 nm to 100 nm, in a range from 1 nm to 50 nm, in a range from 1 nm to 30 nm, in a range from 2 nm to 50 nm, in a range from 2 nm to 30 nm, in a range from 5 nm to 50 nm, and even in a range from 10 nm to 30 nm.

3D. The method of Exemplary Embodiment 1D, wherein layer(s) comprising platinum each independently have a planar equivalent thickness in a range from 0.2 nm to 50 nm (in some embodiments, in a range from 0.2 nm to 20 nm, or even 0.2 nm to 10 nm), layers comprising nickel each independently have a planar equivalent thickness in a range from 0.2 nm to 100 nm (in some embodiments, in a range from 0.2 nm to 25 nm, or even 0.2 nm to 10 nm) and layer(s) comprising ruthenium each independently have a planar equivalent thickness in a range from 0.01 nm to 20 nm (in some embodiments, in a range from 0.01 nm to 10 nm, 0.01 nm to 5 nm, 0.02 nm to 5 nm, 0.02 nm to 1 nm, or even 0.1 nm to 1 nm).

4D. The method of any preceding D Exemplary Embodiment, further comprising annealing the catalyst.

[0050] Advantages and embodiments of this invention are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention. All parts and percentages are by weight unless otherwise indicated. Examples

Preparatory Example A

[0051] Microstructured whiskers employed as catalyst supports were made according to the process described in U.S. Pat. Nos. 5,338,430 (Parsonage et al.), 4,812,352 (Debe), and 5,039,561 (Debe), incorporated herein by reference, using as substrates the microstructured catalyst transfer substrates (or MCTS) described in U.S. Pat. No. 6, 136,412 (Spiewak et al.), also incorporated herein by reference. Perylene red pigment (i.e., N,N'-di(3,5-xylyl)perylene-3,4:9,lO-bis(dicarboximide)) (C.I. Pigment Red 149, also known as“PR149”, obtained from Clariant, Charlotte, NC) was sublimation vacuum coated onto MCTS with a nominal thickness of 200 nm, after which it was annealed. After deposition and annealing, highly oriented crystal structures were formed with large aspect ratios, controllable lengths of about 0.8 micrometer, widths of about 0.03 micrometer and areal number density of about 50 whiskers per square micrometer, oriented substantially normal to the underlying substrate. The combined surface area of the whiskers and the backing was estimated to be about 5.5 cm ² per cm ² planar substrate area.

[0052] Nanostructured thin film (NSTF) catalyst layers were prepared by sputter coating catalyst films sequentially using a DC-magnetron sputtering process onto the layer of microstructured whiskers. A vacuum sputter deposition system was used with typical Ar sputter gas pressures of about 5 mTorr (0.66 Pa), and individual 12.7 cm x 38.1 cm (5-inch x l5-inch) rectangular Pt and Ni sputter targets were used. The coatings were deposited by using ultra high purity Ar as the sputtering gas. A single Pt layer with planar equivalent thickness of about 0.25 nm was first deposited onto the whiskers on MCTS from a pure Pt target. Next, a single Ni layer with planar equivalent thickness of about 0.31 nm was deposited from a pure Ni target. The Pt and Ni deposition processes were repeated 50 times, resulting in an areal loading of about 0.0275 mgp _t /cm ² The targeted individual Pt and Ni layer thicknesses were calculated to yield an overall composition of 37.2 at.% Pt and 62.9 at.% Ni for the combined layers. A total of about 50 linear feet of catalyzed whiskers on MCTS substrate were generated. The targeted composition of the Preparatory Example is listed in Table 1, below.

Table 1

[0053] The Preparatory Example A catalyst material’s calculated planar equivalent thicknesses and the thickness of the catalyst material on the whisker support are listed in Table 2, below.

Table 2

[0054] The total planar equivalent thicknesses of the Pt and Ni deposited was 28.55 nm. When deposited onto the whisker-coated baking, the total Pt and Ni thickness on the support was 5.19 nm, 5.5 times less than the planar equivalent thickness.

[0055] Representative areas of the electrocatalyst were analyzed for bulk composition using X-Ray

Fluorescence spectroscopy (XRF). Representative catalyst samples were evaluated on MCTS using a wavelength dispersive X-ray fluorescence spectrometer (obtained under the trade designation“PRIMUS II” from Rigaku Corporation, Tokyo, Japan) equipped with a rhodium (Rh) X-ray source, a vacuum atmosphere, and a 20-mm diameter measurement area. Each sample was analyzed three times to obtain the average and standard deviation for the measured Pt and Ni signal intensities, which are proportional to loading. The electrocatalyst’s Pt and Ni loadings were determined by comparing their measured XRF intensities to the XRF intensities obtained with standard NSTF electrocatalysts containing Pt and Ni with known areal loadings. From the XRF-determined Pt and Ni loading, the catalyst’s Pt content (at.% Pt) was calculated, based on the Pt and Ni loadings only. Loading and composition information is provided in Table 3, below.

Table 3

[0056] The Pt content of Preparatory Example A was 35.3 at.% and the Ni content was 64.7 at.%.

[0057] Preparatory Example A material was used as input material for Comparative Example A and Examples 1-3 described below.

Comparative Example A

[0058] Comparative Example A consisted of Preparatory Example A, without any additional deposition.

Typically, two or more nominally identical electrocatalyst samples of a given type were fabricated and characterized as described below.

[0059] The Preparatory Example A electrocatalyst was thermally annealed. Electrocatalyst on MCTS was placed into a quartz tube furnace (obtained under the trade designation“LINDBERG BLUE M” from Thermo Electron Corporation, Waltham, MA) and heated to 340°C under flowing EL. After about a 20- minute temperature ramp, the catalyst was annealed for about 0.5 hour at temperature, and then allowed to cool to room temperature over about a 3-hour period. After cooling to room temperature, the tube furnace was purged with nitrogen for about 15 minutes to remove any remaining EL, after which the catalyst on the substrate was removed from the furnace.

[0060] Without being bound by theory, annealed PtNi electrocatalyst with this composition and loading on NSTF supports is structurally and compositionally homogenous, composed of fused nanoscopic catalyst particles, with an approximate electrocatalyst thickness on the support whisker less than 10 nm.

[0061] The Comparative Example A catalyst and NSTF PtCoMn coated anode catalyst whiskers (0.05 mgp _t /cm ² , Pt69Co ₂ 8Mn ₃ ) on MCTS were then transferred to either side of a 24-micrometer thick proton exchange membrane (obtained under the trade designation“3M PFSA 825EW” (neat) from 3M Company, St. Paul, MN), using a laminator (obtained under the trade designation“HL-l0l” from Chemlnstruments, Inc., West Chester Township, OH) to form a catalyst coated membrane (CCM). The three-layer stack-up was hand fed into the laminator with hot nip rolls at 270°F (l32°C), 150 psi (1.03 MPa) nip, and rotating at the equivalent of 0.5 fpm (0.25 cm/s). Immediately after lamination, the MCTS layers were peeled back, leaving the catalyst coated whiskers embedded into either side of the PEM. The CCM was installed with identical gas diffusion layers (obtained under the trade designation“3M 2979 GAS DIFFUSION LAYERS” from 3M Company) on the anode and cathode in 50 cm ² active area test cells (obtained under the trade designation“50 CM ² CELL HARDWARE” from Fuel Cell Technologies, Inc., Albuquerque, NM) with quad-serpentine flow fields with gaskets selected to give 10% compression of the gas diffusion layers. The Comparative Example catalyst was evaluated as the fuel cell cathode.

[0062] After assembly, the test cells were connected to a test station (obtained under the trade designation “SINGLE FUEL CELL TEST STATION” from Fuel Cell Technologies, Inc.). The MEA was then operated for about 40 hours under a conditioning protocol to achieve apparent steady state performance. The protocol consisted of repeated cycles of operational and shutdown phases, each about 40 and 45 minutes in duration, respectively. In the operational phase, the MEA was operated at 75°C cell temperature, 70°C dewpoint, 101/101 kPaA H2/Air, with constant flow rates of 800 and 1800 standard cubic centimeters per minute (seem) of ¾ and air, respectively. During the 40-minute operational phase, the cell voltage was alternated between 5-minute-long polarization cycles between 0.85 V and 0.25 V and 5-minute-long potential holds at 0.40 V. During the 45-minute shutdown phase, the cell potential was set to open circuit voltage, ¾ and air flows to the cell were halted, and the cell temperature was cooled towards room temperature while liquid water was injected into the anode and cathode cell inlets at 0.26 g/min. and 0.40 g/min., respectively.

[0063] After conditioning the MEAs, the electrocatalysts were characterized for relevant beginning of life (BOL) characteristics, including catalyst mass activity, specific surface area, specific activity, and operational performance under relevant H2/Air test conditions, described as follows.

[0064] The cathode oxygen reduction reaction (ORR) absolute activity was measured with saturated 150 kPaA H2/O2, 80°C cell temperature for 1200 seconds at 900 mV vs. the 100% ¾ reference/counter electrode. The ORR absolute activity (A/cm ² or mA/cm ² ) was obtained by adding the measured current density after 1050 seconds of hold time and the electronic shorting and hydrogen crossover current densities, estimated from 2 mV/s cyclic voltammograms measured with N2 fed to the working electrode instead of O2. The electrocatalyst mass activity, a measure of the catalyst activity per unit precious metal content, is calculated by dividing the corrected ORR absolute activity (A/cm ² _pianar ) by the cathode Pt areal loading (mg/cm ² ) to obtain the mass activity (A/mgp _t ). The mass activity of the Comparative Example A is plotted in FIG. 3 and listed in Table 4, below. Table 4

[0065] The cathode catalyst surface enhancement factor (SEF, m ² p _t /m ² pi _anar or analogously cm ² p _t /cm ² pi _anar ) was measured via cyclic voltammetry (100 mV/s, 0.65 V-0.85 V, average of 100 scans) under saturated 101 kilopascals absolute pressure (kPaA) H2/N2 and 70°C cell temperature. The SEF was estimated by taking the average of the integrated hydrogen underpotential deposition (HUPD) charge (pC/cm ² _pianar ) for the oxidative and reductive waves and dividing by 220 microC/cm ² p _t . The electrocatalyst’s specific surface area (m ² p _t /g _pt ), a measure of catalyst dispersion, was calculated by dividing the SEF (m ² p _t /m ² _pianar ) by the areal Pt loading (gp _t /m ² _pianar ). The specific area is plotted in FIG. 4 and reported in Table 4, above.

[0066] The cathode catalyst oxygen reduction specific activity was calculated by dividing the corrected

ORR absolute activity (A/cm ² _pianar ) by the SEF (cm ² p _t /cm ² _pianar ) to obtain the specific activity expressed in (A/cm ² p _t ), or after unit conversion as mA/cm ² p _t (multiply (A/cm ² ) by 1000 mA per A). The specific activity is plotted in FIG. 5 and reported in Table 4, above. The specific activity is a measure of catalyst activity per unit catalyst surface area, a measure of fundamental catalyst activity.

Example 1

[0067] Example 1 catalyst was prepared and characterized similarly to Comparative Example A, except that prior to thermal annealing, ruthenium was deposited onto the surface of the Preparatory Example A catalyst.

[0068] A vacuum sputter deposition system was used to deposit ruthenium with typical Ar sputter gas pressures of about 5 mTorr (0.66 Pa), and an individual 12.7 cm x 38.1 cm (5-inch x l5-inch) rectangular Ru sputter target. Prior to sputter depositing ruthenium onto the Preparatory Example A catalyst, gravimetric calibration of the ruthenium sputter deposition was conducted to determine areal ruthenium loadings as a function of target power at fixed web speed. Table 5, below, summarizes the calibration data generated, and this data was used to estimate deposition conditions (target power, web speed, and number of passes) needed to deposit specific areal loadings of ruthenium. Table 5

[0069] Using the Table 5 calibration data, deposition conditions were determined which would result in 0.20 microgram/cm ² ruthenium. A 2-lineal foot section of the Preparatory Example A catalyst was loaded into the sputter system, and ruthenium coating was deposited by using ultra high purity Ar as the sputtering gas. The Example 1 catalyst’s composition, based on the targeted Pt, Ni, and Ru areal loadings, is summarized in Table 1, above. The Example 1 targeted catalyst composition was 36.95 at.% Pt, 62.53 at.% Ni, and 0.52 at.% Ru. The Example 1 catalyst’s calculated planar equivalent thicknesses and thicknesses on the support are summarized in Table 2, above. The total planar equivalent thicknesses of the Pt and Ni deposited was 28.55 nm and the total planar equivalent thickness of Ru deposited was 0.16 nm. When deposited onto the whisker-coated baking, the total Pt and Ni thickness on the support was 5.19 nm and the total Ru thickness on the support was 0.03 nm.

[0070] After Ru deposition, the catalyst was thermally annealed and characterized similarly to Comparative Example A. The catalyst’s mass activity, specific area, and specific activity are listed in Table 3, above, and plotted in FIGS. 3, 4, and 5, respectively.

Examples 2 and 3

[0071] Examples 2 and 3 catalysts were prepared and characterized similarly to Example 1, but the ruthenium deposition conditions were modified.

[0072] The targeted ruthenium areal loadings were 0.4 and 2.1 microgram/cm ² for Examples 2 and 3, respectively. The catalysts composition, based on the targeted Pt, Ni, and Ru areal loadings, is summarized in Table 1, above. The targeted catalyst composition for Example 2 and 3 were, respectively, 36.76 and 35.22 at.% Pt, 62.21 and 59.59 at.% Ni, and 0.52 and 5.19 at.% ruthenium. The catalysts’ mass activities, specific areas, and specific activities are listed in Table 3, and plotted in FIGS. 3, 4, and 5, respectively.

Preparatory Example B

[0073] Preparatory Example B was prepared and characterized similarly to Preparatory Example A, except that the targeted Pt and Ni loadings were 28 and 15 micrograms/cm ² , respectively. The catalysts composition, based on the targeted Pt and Ni areal loadings, is summarized in Table 1, above. The targeted catalyst composition for Preparatory Example B was 35.96 at.% Pt and 64.04 at.% Ni. Preparatory Example B material was used as input material for Comparative Example B and Examples 4-9 described below.

Comparative Example B

[0074] Comparative Example B was prepared and characterized similarly to Comparative Example A, except that Preparatory Example B catalyst was used instead of Preparatory Example A catalyst. The catalysts’ mass activities, specific areas, and specific activities are listed in Table 3, above, and plotted in FIGS. 3, 4, and 5, respectively.

Examples 4-9

[0075] Examples 4-9 were prepared and characterized similarly as Example 1, except that Preparatory Example B catalyst was used instead of Preparatory Example A, and the Ru deposition conditions were modified to yield different amounts of Ru. The targeted Ru contents for Examples 4-9 were 0.20, 0.40, 0.82, 2.10, 2.55, and 4.44 microgram/cm ² , respectively. The targeted catalyst composition for Example 4-9 were, respectively, 35.79, 35.61, 35.25, 34.18, 33.82, and 32.40 at.% Pt, 63.72, 63.41, 62.76, 60.87, 60.23, and 57.69 at.% Ni, and 0.49, 0.98, 1.99, 4.95, 5.95, and 9.92 at.% ruthenium. The catalysts’ mass activities, specific areas, and specific activities are listed in Table 3, above, and plotted in FIGS. 3, 4, and 5, respectively.

Results

[0076] FIG. 3 and Table 3, above, summarize the measured mass activity for Comparative Examples A and B and Examples 1-9. The mass activities of Comparative Examples A and B were 0.38±0.03 and 0.38±0.08 A/mg. The mass activities of Examples 1-9 were 0.38±0.0l, 0.56±0.07, 0.36±0.00, 0.43±0.08, 0.53±0. l0, 0.46±0.06, 0.38±0.2l, 0.42±0.04, and 0.38±0.06 A/mg, respectively. The mass activities of Examples 2, 4, 5, 6, and 8, with targeted Ru contents of 1.03, 0.49, 0.98, 1.99, and 5.95 at.% were higher than the Comparative Examples which did not contain Ru. [0077] FIG. 4 and Table 3, above, summarize the specific surface area of Comparative Examples A and B and Examples 1-9. The specific areas of Comparative Example A and Examples 1, 2, and 3 were 18.4+0.1, 17.9T0.3, 18.8+1.3, and 16.7T0.4 m ² /g. The specific areas of Comparative Example B and Examples 4, 5, 6, 7, 8, and 9 were 16.9T0.4, 17.6+0.1, 18.4+1.0, 14.1+3.0, 15.8+2.5, and 14.6T2.6 m ² /g. The specific areas of Comparative Examples A and B, which did not contain Ru, ranged from 17.5+0.4 to 18.4+0.1 m ² /g. Between 0.49-1.99 at.% Ru, the specific areas of Examples 1, 2, 4, 5, and 6 ranged from 16.9+0.4 to 18.8 m ² /g, similar to Comparative Examples A and B. Between 4.95 and 9.92 at.% Ru, the specific areas of Examples 3, 7, 8, and 9 ranged from 14.1+3.0 to 16.7+0.4 m ² /g, lowerthan Comparative Examples A and B.

[0078] FIG. 5 and Table 3, above, summarize the measured specific activity of Comparative Examples A and B and Examples 1-9. The specific activities of Comparative Examples A and B were 2.08+0. 13 and 2.17+0.25 mA/cm ² p _t , respectively. The specific activities of Examples 1-9 were 2.14+0.11, 2.96±0. l4, 2.18T0.06, 2.55±0.39, 3.00±0.56, 2.42T0.19, 2.60±0.93, 2.66T0.18, and 2.67±0.08 mA/cm ² _Pt , respectively. The specific activities of Examples 1, 2, and 3, with 0.52, 1.03, and 5.19 at.% Ru, were higher than the specific activity of Comparative Example A which did not contain Ru. The specific activities of Examples 4, 5, 6, 7, 8, and 9, with 0.49, 0.98, 1.99, 4.95, 5.95, and 9.92 at.% Ru, were higher than the specific activity of Comparative Example B.

[0079] Foreseeable modifications and alterations of this disclosure will be apparent to those skilled in the art without departing from the scope and spirit of this invention. This invention should not be restricted to the embodiments that are set forth in this application for illustrative purposes.