# Patent

## Title
Catalyst assembly and method of making the same

## Abstract

In one embodiment, the catalyst assembly includes a two-dimension (2-D) extensive catalyst having a catalyst crystal plane; and a substrate supporting the 2-D extensive catalyst and having a substrate crystal plane in substantial alignment with the catalyst crystal plane. In certain instances, the catalyst crystal plane includes first and second adjacent catalyst atoms defining a catalyst atomic distance, the substrate crystal plane includes first and second adjacent substrate atoms defining a substrate atomic distance, a percent difference between the catalyst and substrate atomic distances is less than 10 percent.

## Background
BACKGROUND
1. Technical Field
The present invention relates to a catalyst assembly and method of making the same.
2. Background Art
Fuel cells are potential low emission energy sources to power vehicles. Existing fuel cell catalysts include platinum (Pt) nano-particles on carbon support. These catalysts are susceptible to catalyst dissolution and/or agglomeration, often require excessive precious catalyst loading, and therefore are cost-inefficient in general.
SUMMARY
According to one aspect of the present invention, there is provided a catalyst assembly. In one embodiment, the catalyst assembly includes a two-dimension (2-D) extensive catalyst having a catalyst crystal plane; and a substrate supporting the 2-D extensive catalyst and having a substrate crystal plane in substantial alignment with the catalyst crystal plane. In certain instances, the catalyst crystal plane includes first and second adjacent catalyst atoms defining a catalyst atomic distance, the substrate crystal plane includes first and second adjacent substrate atoms defining a substrate atomic distance, a percent difference between the catalyst and substrate atomic distances is less than 10 percent. In certain other instances, the catalyst and substrate crystal planes are positioned next to each other. In certain particular instances, the 2-D extensive catalyst has a thickness dimension of 2 to 20 atomic layers.
In another embodiment, the substrate is two-dimension (2-D) extensive such that the 2-D extensive catalyst and the substrate are positioned next to each other in a layer-layer configuration. In yet another embodiment, the catalyst assembly is configured as a plurality of core-shell particles, wherein the 2-D catalyst is the shell and the substrate is the core.
In yet another embodiment, the substrate and the 2-D extensive catalyst have at least one crystal plane in common, the common crystal plane being a (111) crystal plane, a (110) crystal plane, a (001) crystal plane, and/or a (0001) crystal plane.
In yet another embodiment, the substrate includes one or more (111) oriented metal elements including Ag, Al, Au, Cu, Ir, Pd, and Rh; one or more (011) oriented metal elements including Mo, Nb, Ta, W, Os, Re, and Ru; one or more (0001) oriented metal elements including Ti; and combinations and alloys thereof.
In yet another embodiment, the substrate includes one or more metal oxides including (100) oriented TiO2, (111) oriented NbO, SrTiOx, and YSZ; one or more metal nitrides including (111) oriented TiN; one or more carbides including (111) oriented TiC and (0001) oriented WC; and combinations thereof.
In yet another embodiment, the substrate includes one or more graphene-containing structures including graphite, graphene, metal sulfides, selenides, and silicides; one or more aromatic-ring structured polymeric materials including phthalocyanines, porphyrins, Schiff bases, metal-N4 macrocycles, and metal-organic frameworks; and combinations thereof.
In yet another embodiment, the substrate is electronically conductive.
In yet another embodiment, the substrate is a mesh including one or more pores for transporting water molecules. In certain instances, the substrate includes a mesh support and seeding material coated on the mesh support.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1A depicts a catalyst assembly according to one embodiment;
FIGS. 1B1 and 1B2 collectively depict a schematic view showing atomic distance and atomic distance variation directed to the catalyst assembly of FIG. 1B;
FIGS. 2A and 2B depict various catalyst growth modes for forming a catalyst assembly according to another embodiment;
FIGS. 3A to 3C depict free surface energy values of certain materials for forming a catalyst assembly according to yet another embodiment;
FIG. 4 depicts an exemplary crystal configuration of Pt;
FIG. 5 depicts exemplary materials suitable for forming a catalyst assembly according to yet another embodiment;
FIG. 6 depicts atomic distance variation percent values of certain materials for forming a catalyst assembly according to yet another embodiment;
FIG. 7 depicts exemplary elements included in certain ceramic materials for forming a catalyst assembly according to yet another embodiment;
FIG. 8 depicts exemplary structure of graphene as included in materials for forming a catalyst assembly according to yet another embodiment;
FIG. 9 depicts an exemplary benzene-ring structure included in materials for forming a catalyst assembly according to yet another embodiment;
FIG. 10 depicts an exemplary mesh structure included in a catalyst assembly according to yet another embodiment;
FIGS. 11A to 11E depict non-limiting examples of particularized catalyst assembly according to yet another embodiment;
FIGS. 12A to 12C depict several ring structures used in materials forming a catalyst assembly according to yet another embodiment; and
FIG. 13 depicts non-limiting examples of particle morphologies of a substrate according to yet another embodiment.



DETAILED DESCRIPTION
As required, detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention that may be embodied in various and alternative forms. The figures are not necessarily to scale; some features may be exaggerated or minimized to show details of particular components. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for teaching one skilled in the art to variously employ the present invention.
Except where expressly indicated, all numerical quantities in this description indicating amounts of material or conditions of reaction and/or use are to be understood as modified by the word “about” in describing the broadest scope of the present invention.
The description of a group or class of materials as suitable for a given purpose in connection with one or more embodiments of the present invention implies that mixtures of any two or more of the members of the group or class are suitable. Description of constituents in chemical terms refers to the constituents at the time of addition to any combination specified in the description, and does not necessarily preclude chemical interactions among constituents of the mixture once mixed. The first definition of an acronym or other abbreviation applies to all subsequent uses herein of the same abbreviation and applies mutatis mutandis to normal grammatical variations of the initially defined abbreviation. Unless expressly stated to the contrary, measurement of a property is determined by the same technique as previously or later referenced for the same property.
The present invention, in one or more embodiments, provides a substrate and a method of forming the substrate to support the formation of pseudo-bulk catalysts that are 2-D extensive. The substrate may be formed from pre-selected materials with certain criteria met. Non-limiting examples of the selection criteria include substrate crystal symmetry, both translational and rotational, relative to a desirable crystal plane of the pseudo-bulk catalyst; and/or atomic distance variation between the pseudo-bulk catalyst and the substrate. In one variation, the pseudo-bulk catalyst may be presented as a 2-D extensive thin film supported on the substrate to form a layer-to-layer catalyst assembly. In another variation, the substrate can be configured as a plurality of nano-particles for seeding the growth of the pseudo-bulk catalyst to form particularized catalyst assembly. The particularized catalyst assembly may then be spray coated onto a preformed mesh support. Thus formed catalyst assemblies are believed to have enhanced catalytic stability while maintaining desirable cost benefits.
According to one aspect, and as illustratively depicted in FIG. 1A, there is provided a catalyst assembly 100 with relatively increased catalyst reliability and cost-efficiency. The catalyst assembly 100 includes a 2-D extensive catalyst 102 supported on a substrate 104. The 2-D extensive catalyst 102 includes one or more catalyst crystal planes illustratively shown as layers of catalyst atoms 106 arranged in the x-y dimensions. The substrate 104 includes one or more substrate crystal planes illustratively shown as layers of substrate atoms 108 arranged in the x-y dimensions. The 2-D extensive catalyst 102 is presented in a pseudo-bulk configuration such that the catalytic metals behave, relative to conventional nano-particles, more like bulk metals. In this pseudo-bulk configuration, the 2-D extensive catalyst 102 is presented as being x-axis and y-axis extensive relative to the z-axis. In certain instances, the thickness dimension along the z-axis may be in a range of 2 to 20 atomic layers. Without wanting to be limited to any particular theory, it is believed that the 2-D extensive catalyst 102 of the catalyst assembly 100 is crystallographically oriented such that the catalytic activities of the 2-D extensive catalyst 102 may be effectively utilized.
In one or more embodiments, the term “crystallographically oriented” refers to that the surface of the 2-D extensive catalyst such as the 2-D extensive catalyst 102 of FIG. 1A is aligned or arranged according to a particular crystal plane, such as a (111) plane, a (110) plane, or a (001) plane.
In one or more embodiments, the catalyst crystal plane of the 2-D extensive catalyst 102 and the substrate crystal plane of the substrate 104 are substantially aligned to facilitate the crystallographical orientation of the catalyst atoms 106. In certain instances, the term “substantially aligned” refers to an atomic distance difference between the 2-D extensive catalyst 102 and the substrate 104 is less than 10 percent, 8 percent, 6 percent, 4 percent, or 1 percent.
In one or more embodiments, and as depicted in FIGS. 1B1 and 1B2, term “atomic distance” for the 2-D catalyst 102 and the substrate 104 may be represented, respectively, as the distance ADcatalyst between any two adjacent catalyst atoms 106 and the distance ADsubstrate between any two adjacent substrate atoms 108. The term “atomic distance percent difference” refers to (ADcatalyst−ADsubstrate)/ADsubstrate×100%.
In certain instances, and as depicted in FIG. 1A, the 2-D extensive catalyst 102 is atomically smooth, for instance, is atomically smooth at the atomic level, and has 2 to 20 atomic layers of crystallographically oriented catalyst crystal plane. In certain particular instances wherein the 2-D extensive catalyst 102 includes platinum (Pt), a relatively high electro-catalytic activities crystal plane is (111) and (110) for Pt, and (111) for platinum nickel alloy Pt3Ni.
In yet another embodiment, the substrate 104 and the 2-D extensive catalyst 102 share at least one common crystal plane, wherein the substrate 104 has a (111) crystal plane, a (110) crystal plane, and/or a (0001) crystal plane.
In yet another embodiment, and as depicted in FIGS. 2A and 2B, the catalyst atoms 106 may be deposited onto the substrate 104 via any suitable methods including chemical vapor deposition, physical vapor deposition, chemical or electrochemical deposition or a combination thereof. Without wanting to be limited to any particular theory, it is believed that the 2-D extensive catalyst 102 nucleates on the substrate 104 via the first few catalyst atoms being deposited as the nuclei, wherein the size and orientation of the nuclei may be determined by the materials characteristics of the substrate and/or the catalyst. These materials characteristics may include differences in crystal symmetry, translational and/or rotational, free surface energy, and interfacial energy.
In one or more embodiments, crystal orientation for both the 2-D extensive catalyst 102 and the substrate 102 may be determined by X-Ray Diffraction; and atomic distance percent difference for both the 2-D extensive catalyst 102 and the substrate 104 may be determined by SEM (Scanning Electron Microscopy) and/or TEM (Transmission Electron Microscopy) imaging analysis.
In one or more embodiments, it has been discovered that the thermodynamical growth mode is a function of the atomic distance variation and the relative differences of free surface energies between the 2-D extensive catalyst 102 and the substrate 104. As depicted in FIGS. 2A and 2B, non-limiting examples of the thermodynamical growth mode include: 1) layer-by-layer growth generally shown at 2a1 with a resulting catalyst assembly shown at 2b1, when the surface free energy of the substrate 104 is greater than that of the 2-D extensive catalyst 102, and the atomic distance variation is less than 0.4 percent; 2) layer-by-layer initially followed by island growth mode generally shown at 2a2 with a resulting catalyst assembly shown at 2b2, when surface free energy of the substrate 104 is greater than that of the 2-D extensive catalyst 102 and combination of the atomic distance variation and free surface energies ratio between the 2-D extensive catalyst 102 and the substrate 104 fall above the dotted line in the first quadrant; and 3) an island mode generally shown at 2a3 with a resulting catalyst assembly shown at 2b3.
FIGS. 3A to 3C depict relative free surface energies or free surface energies of many candidate materials for forming the substrate 104 relative to Pt. Free surface energy of Pt is anisotropic in that Pt in different atomic configurations may have different free surface energy values. Non-limiting examples of free surface energy values for Pt include 2700 mJ/m2 for Pt (111), 3240 mJ/m2 for Pt (110), and 2980 mJ/m2 for Pt (100). FIG. 3A depicts free surface energy differential of several metal elements, in their closest atomic arrangements, relative to free surface energy of (111) Pt. FIG. 3B depicts free surface energies of several selected oxides, graphite, and polymers. FIG. 3C depicts free surface energies of several selected carbides, nitrides and borides. As referenced in FIG. 3A, the y-axis represents the free surface energy difference between the Pt (111) and that of the substrate crystal surface that is commensurate with the Pt (111) in terms of crystal symmetry, and their lattice distance variation is less than 10%; while in FIGS. 3B and 3C, the y-axis represents the free surface energies of substrate materials. The x-axis refers to the exemplary elements and their related materials.
Without wanting to be limited to any particular theory, based on surface free energy and atomic distance variation, it is believed that certain materials, including certain oxides, graphene-structured materials, polymeric materials, metals, carbides, nitrides, and borides, which can be used to form the substrate 104 for growing and supporting the 2-D extensive catalyst 102 such as a pseudo-bulk Pt catalyst.
It has been discovered, in one or more embodiments, that pseudo-bulk catalyst nucleation and growth are affected by surface energies, atomic symmetry and/or atomic distance variation; that surface energy differences between substrates and catalysts also affect the catalyst mode of growth. For pseudo-bulk catalyst such as the 2-D extensive catalyst 102 of FIG. 1A wherein the z-axis is of several atomic layer in thickness, crystal orientation of the 2-D extensive catalyst 102 may be dependent upon one or more of the following two criteria. First, crystal symmetry, both translational and rotational, of the substrate 104 is compatible with the crystal symmetry of a crystal plane of the 2-D extensive catalyst 102. Second, atomic distance variation between the substrate 104 and the 2-D extensive catalyst 102 are within certain specified ranges. For Pt and Pt alloys cathode catalyst, the most electro-catalytically active planes for ORR are (110) and (111). Shown in FIG. 4 is one exemplified atomic arrangement of Pt (111) plane with six nearest Pt neighbors at a distance of 2.77 Å.
In certain instances, suitable materials for forming the substrate may include certain metals. These metals may include, and as depicted in FIG. 5, metal elements and alloys that have simple crystal symmetry compatible with that of Pt (111), especially those with face centered cubic (FCC) structure, the same as Pt, where (111) is the most densely packed crystal plane; metals with body centered cubic (BCC) structure having (110) as the most densely packed crystal plane; and metals with hexagonal close packed (HCP) structure having (0001) as the most densely packed crystal plane.
In certain other instances, suitable materials for forming the substrate may include elements that have the same atomic symmetry as that of Pt (111), and their atomic distance on the closest packaged plane falls within 10% of that of Pt (111) as shown in FIG. 6 and Table 1. For metallic substrate, its crystal symmetry and atomic distance can be tailored by alloying and processing, leading to many potential metallic alloys that could be used as the substrate materials for pseudo-bulk catalyst development, provided the substrate crystal plane could be grown in the desired crystal orientation.










TABLE 1








Atomic Distance



Element
Variation Percent



















Ag
3.61



Al
3.13



Au
3.85



Cu
−8.52



Ir
−2.18



Pd
−0.86



Rh
−3.15



delta Mn
−3.97



Mo
−1.76



Nb
2.96



Ta
3.12



beta-Ti
3.14



V
−5.91



W
−1.20



Os
−1.40



Re
−0.46



Ru
−2.58



alpha-Ti
5.98










In certain other instances, suitable materials for forming the substrate may include one or more ceramic compounds. Ceramic compounds are a combination of one or more metallic elements such as Fe and Co included under the lighter strip shading with one or more nonmetallic elements such as C and N included under the heavier strip shading as shown in FIG. 7. In certain instances, ceramic compounds may be classified into oxides, carbides, nitrides, borides, and graphene-structured materials and their solid solutions.
Without wanting to be limited by any particular theory, it is believed that certain ceramic compounds have crystal structures and/or atomic arrangements that are compatible to those of precious catalyst metals such as Pt. In oxides, for instance, oxygen (O) atoms occupy the crystal lattice sites, and the crystal-symmetry-compatible O plane may act as the substrate plane to template crystographically oriented (111) Pt atomic layer catalyst films. For instance also, in metal carbides, nitrides, and borides, the lighter constitutive elements C, N, and B occupy the interstitial sites in the crystal lattice, accompanied by lattice expansion and sometimes also transformation in crystal structure. The atomic plane formed by metal atoms with compatible symmetry will be the plane to orient the (111) Pt catalyst. Non-limiting examples of these compounds are listed in Table 2.













TABLE 2









TiO2
Tetragonal
(100)
O—O
2.78 A°



NbO
FCC
(111)
O—O
2.97 A°



α-Al2O3
RHO
(0001)
O—O
2.53 A°



WC
Hexagonal
(0001)
W—W
2.90 A°



TiN
FCC
(111)
Ti—Ti
3.03 A°



TiC
FCC
(111)
Ti—Ti
3.04 A°










In one or more embodiments, suitable materials for forming the substrate 104 include elemental carbon, metal sulfides, selenides, silicides, or combinations thereof. Without wanting to be limited to any particular theory, it is believed that elemental carbon, metal sulfides, selenides, and/or silicides possess the crystal structure of graphene as shown in FIG. 8, where the crystal symmetry on the layered plane is compatible with Pt (111). In certain instances when the atomic distance variation is suitable, such as in the case of graphite, these materials help grow pseudo-bulk Pt (111) catalyst of several atomic layer thick, consistent with the observation of 80% of Pt is (111) plane in 2-3 nm Pt nano-particles on amorphous carbon.
In one or more embodiments, suitable materials for forming the substrate 104 include polymeric materials including H and one or more of elements B, C, N, O, F, P, and Si, as depicted in FIG. 7. Particularly useful polymeric materials may include one or more aromatic rings, such as benzene-ring structure as depicted in FIG. 9. Without wanting to be limited to any particular theory, it is believed that in this design, the resultant substrate is provided with the atomic symmetry that is compatible with that of Pt (111), and the atomic distance is relatively close to the atomic distance between Pt atoms along the (111) crystal plane.
In certain instances, the polymeric materials include copolymers such as di-block or tri-block copolymers, which can be tailored into thin layered substrates compatible with the 2-D extensive catalyst 102. In certain particular instances, the polymeric materials can be rendered electronically conductive, as in conductive polymers, the resultant conductive substrate has the additional benefit of reducing resistance losses across the thickness dimension of the 2-D extensive catalyst 102. Non-limiting examples for this type of polymeric materials include molecular or molecular-derived catalysts, which include phthalocyanines, porphyrins, Schiff bases and related derivatives, and Metal-N4 macrocycles (M=Fe, Co, Ni, or Cu), dubbed as oxidative multi-electron transfer catalysts. Other materials, such as metal-organic frameworks with repeated aromatic rings as the linkers could also be candidate substrate materials. In certain other instances, suitable polymeric materials may also include polymers that contain translational and rotational repeat units of aromatic rings that are compatible with those of Pt (111) could serve as substrate materials.
In another aspect of the present invention, there is provided a method of selecting substrates for supporting pseudo-bulk catalyst such as 2-D extensive catalyst 102. In certain instances, materials for forming the substrate 104 are selected to have compatible crystal symmetry, both rotational and translational, with that of a desirable crystal plane of the 2-D extensive catalyst 102. In certain other instances, materials for forming the substrate 104 are selected such that atomic distance variation between the catalyst and the substrate is within a certain limit to ensure the growth of atomically smooth 2-D extensive catalyst of several atomic layers.
It has also been discovered that water management can be advantageously managed with the catalyst assembly 100 according to one or more embodiments. In certain instances, the substrate is further configured to have a mesh structure such as one generally shown in FIG. 10. Without wanting to be limited to any particular theory, it is believed that the substrate 104 in this mesh design helps facilitate water management by reducing unnecessary water accumulation while supporting the 2-D extensive catalyst 102. Non-precious metal catalytic substrate can itself form the mesh or can be applied onto a pre-existing mesh structure in a film or coating. The molecular or molecular-derived non-precious metal catalytic substrate may include one or more materials including aromatic ring containing structures and graphene containing structures as discussed herein elsewhere. The 2-D extensive precious metal catalyst 102 such as a crystallographically oriented Pt or Pt alloy catalyst can be grown onto the mesh substrate with a thickness of 2 to 20 atomic layers.
The mesh structure can be made with any suitable methods. A non-limiting example of the methods for making the mesh structure is illustrated as follows. In this example, the mesh structure is generated via processing one or more block-copolymers as shown in FIGS. 11A to 11F. The block-copolymers may include aromatic-ring structured polymers, which lie flat along a mesh plane. The resultant mesh structure is then used to seed and template the growth of pseudo-bulk catalyst. In certain instances, the mesh structure may include one or more polymers that are also electronically conductive, and the resultant mesh structure can reduce the electric resistance loss in the catalyst layers. In certain other instances, the polymer-based mesh structure can be made flexible, suitable for direct inclusion into an electrochemical environment such as one for the fuel cell applications.
In yet another embodiment, the mesh structure is formed of a mesh support and a substrate coating disposed onto the mesh support. The mesh support can be preformed to have appropriate pore sizes for water transportation, and can optionally be a part of the catalyst layer with suitable material flexibility, corrosion resistance, and electric conductivity as detailed herein. Once formed, the mesh support can then be processed to incorporate a substrate coating. A non-limiting example of the substrate coating can be formed from a layer of aromatic-ring structured polymer, a single-layer graphene, or some non-precious metal catalysts such as metal oxides, carbides, nitrides, or molecular-based non-precious metal catalysts such as metalloporphyrins with the suitable atomic arrangements and atomic distance variation relative to those of Pt-based catalysts. Once the mesh substrate is formed for use as a seeding template, Pt-based catalyst is then generated on top of the seeding template via any suitable processing methods. Non-limiting examples of the processing methods include chemical vapor deposition, physical vapor deposition, wet chemical deposition, electro-chemical deposition methods, and a combination thereof. Several examples for forming the seedling template can be found in FIGS. 12A to 12C.
In yet another embodiment, the seeding template can be formed to have various morphologies. Non-limiting examples of the morphologies are depicted in FIG. 13. Without wanting to be limited to any particular theory, it is believed that these various morphologies help enhance the effective electro-catalytic surface area of the catalysts disposed thereupon.
In certain instances, the substrate 104 can be configured as substrate particles, which can then be disposed on top of a pre-formed mesh support via suitable methods such as nano-molding in conjunction with processing of polymeric mesh structure through any suitable methods such as nanolithography, or through coating onto an existing mesh. Once this mesh substrate is formed, catalysts such as Pt catalysts deposited onto the mesh substrate to have the psedo-bulk characteristics. Without wanting to be limited to any particular theory, it is believed that this design is provided with the additional benefits of providing increased surface area on a fixed geometric surface area. In certain instances, the mesh substrate particles can also be included as part of the catalyst assembly or can be removed after the completion of the seeding process. In certain particular instances, the mesh substrate particles have 2-D elongated with a L/D (length to diameter ratio) of between 2 and 20.
In certain other instances, particles of the substrate can be pre-coated with crystallographically oriented catalysts such as Pt catalysts to provide a catalyst with enhanced electro-catalytic activities. Without wanting to be limited to any particular theory, it is believed that one or more factors are involved in the enhanced electro-catalytic activities; and the factors include increased electro-catalytically active surface plane, increased effective surface area, and improved substrate-catalyst d-band interaction through substrate-catalyst chemical communications. The thus-formed substrate-catalyst assembly can be applied as an ink and disposed onto the mesh support. Contrary to conventional catalyst nano-particles such as Pt nano-particles on carbon support, particles of the substrate-catalyst assembly according to one or more embodiments are 2-D extensive such that a substantial portion or the entirety of the particles each have 2 to 20 atomic layers of catalyst in thickness dimension.
In certain instances, the substrate includes one or more metallic materials, including (111) oriented FCC metals such as Ag, Al, Au, Cu, Ir, Pd, and Rh; (011) oriented BCC metals such as Mo, Nb, Ta, W, Os, Re, Ru; and (0001) oriented HCP metals such as Ti, and metallic alloys thereof having atomic symmetry and atomic distance variation compatible with one or more desirable electro-catalytically active crystal planes.
In certain instances, the substrate includes one or more ceramic materials, including oxides such as (0001) oriented alpha-Al2O3 
In certain instances, the substrate includes one or more metal oxides, such as (100) oriented TiO2, (111) oriented NbO, SrTiOx and YSZ.
In certain instances, the substrate includes one or more metal nitrides, such as (111) oriented TiN; carbides such as (111) oriented TiC, and (0001) oriented WC.
In certain instances, the substrate includes one or more materials that evidence a graphene-structured surface, which can include graphite, graphene, metal sulfides, selenides, silicides, and boron nitrides.
In certain instances, the substrate includes one or more aromatic-ring structured polymeric materials; molecular or molecular-derived catalysts, which include phthalocyanines, porphyrins, Schiff bases and related derivatives; metal-N4 macrocycles (M=Fe, Co, Ni, or Cu), dubbed as oxidative multi-electron transfer catalysts; metal-organic frameworks with repeated aromatic rings as the linkers.
The following application discloses and claims catalyst assemblies that may be related to the catalyst assembly disclosed and claimed herein: U.S. patent application Ser. No. 12/911,862, filed on Oct. 26, 2010, the entire contents of thereof are incorporated herein by reference.
While the best mode for carrying out the invention has been described in detail, those familiar with the art to which this invention relates will recognize various alternative designs and embodiments for practicing the invention as defined by the following claims.

## Claims

1. A catalyst assembly comprising:
a crystalline substrate of metal oxide, metal nitride and/or carbide and having an atomic distance between first and second adjacent atoms; and
a Pt3Ni catalyst layer of up to 20 atomic layers including an exposed surface layer crystallographically oriented according to a (111) plane, and supported on the crystalline substrate, the atomic distance between two adjacent catalyst atoms and the atomic distance between any two adjacent substrate atoms is less than 10 percent apart.

2. The catalyst assembly of claim 1, wherein the crystalline substrate has a (111) crystal plane, a (110) crystal plane, a (001) crystal plane, and/or a (0001) crystal plane.

3. The catalyst assembly of claim 1, wherein the metal oxide is TiO2, NbO, SrTiOx, and YSZ, the nitride is TiN, and the carbide is TiC.

4. The catalyst assembly of claim 1, wherein the crystalline substrate includes one or more elements of Ag, Al, Au, Cu, Ir, Pd, Rh, Mo, Nb, Ta, W, Os, Re, Ru and/or Ti; one or more graphene-containing structures of graphite, graphene, metal sulfides, selenides, and silicides; one or more aromatic-ring structured polymeric materials of phthalocyanines, porphyrins, Schiff bases, metal-N4 macrocycles, and metal-organic frameworks; and, one or more ceramic materials of alpha-Al2O3.

5. The catalyst assembly of claim 1, wherein the crystalline substrate is electronically conductive.

6. The catalyst assembly of claim 1, wherein the crystalline substrate includes a mesh support and a seeding material coated on the mesh support.