WO2024258828A1

WO2024258828A1 - Composite catalyst providing versatile scaffold for catalyst preparation

Info

Publication number: WO2024258828A1
Application number: PCT/US2024/033364
Authority: WO
Inventors: Lisandra Arroyo Ramirez; James R. Hanrahan; Jeffrey A. Knopf; Jeffrey S. LEDFORD; Tracy L. SIMON
Original assignee: WL Gore and Associates Inc
Current assignee: WL Gore and Associates Inc
Priority date: 2023-06-13
Filing date: 2024-06-11
Publication date: 2024-12-19
Anticipated expiration: 2025-12-13

Abstract

A catalytic article that includes a porous composite with a plurality of support substrate particles non-covalently enmeshed within a porous fibrillated polymer matrix and a catalyst coating deposited on the support substrate particles. Methods for preparing the catalytic article and uses of the catalytic article in reactions are also provided.

Description

COMPOSITE CATALYST PROVIDING VERSATILE SCAFFOLD FOR CATALYST PREPARATION

CROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit of Provisional Application No. 63/472,706, filed June 13, 2023, which is incorporated herein by reference in its entirety for all purposes.

FIELD

[0002] The present disclosure relates generally to compositions, apparatuses, systems, and methods for preparing composite catalysts. More specifically, the disclosure relates to compositions, apparatuses, systems, and methods for the preparation of PTFE composite catalysts which provide a versatile scaffold for catalyst preparation and use.

BACKGROUND

[0003] Catalysts are used in a variety of applications to change chemical composition or to decompose and remove contaminants. A common problem when using a catalyst is easily and stably mounting the catalyst while maximizing the available catalyst area for the reaction between the catalyst and the fluid to be treated. The catalyst may provide the maximum catalyst area in powder or other particle form, but it will not catalyze unless the catalyst particles are arranged so that the fluid to be treated can flow freely throughout the catalyst area.

[0004] Supported catalysts provide a solution to these problems and are preferred for multiphase chemical reactions. They are usually prepared by impregnating a porous high surface area support medium with a salt of the catalytic metal in solution or ion-exchanging atoms of the catalytic metal for certain of those of the support medium.

[0005] Conventional preparation methods used to produce supported catalysts can be complex and unsafe due to the need to handle small particle size catalyst powders. In addition, access of liquid or vapor catalyst precursors to a volume of small catalyst support powder can be poor due to mass transfer limitations. One approach to address some of these challenges involves the use of larger support particles; however, this often results in heterogeneous or poorly dispersed catalysts because the catalyst precursor species cannot fully penetrate the pores of the support before they are deposited onto the support surface.

SUMMARY

[0006] The preparation of uniform, well-dispersed catalyst species supported on small particle sized carriers that are optimum for catalyst performance and regenerability is difficult. The present disclosure provides composite catalysts and methods for producing composite catalysts which can address these challenges by providing an easy to handle, uniformly accessible form of well-dispersed catalyst support particles. Such structures are well suited for liquid or vapor catalyst preparation methods.

[0007] According to a first Embodiment (Embodiment 1 ), the disclosure provides a method including: providing a porous composite including a plurality of support substrate particles non-covalently enmeshed within a porous fibrillated polymer matrix; and applying a catalyst coating to the porous composite such that the catalyst coating is selectively deposited substantially on the support substrate particles; whereby a catalyst coated composite is formed.

[0008] Embodiment 2 is the method of Embodiment 1 , wherein the porous fibrillated polymer matrix includes a polymer having a surface energy of less than 35 dyne/cm.

[0009] Embodiment 3 is the method of any of the preceding Embodiments, wherein the support substrate particles have a surface energy that is at least 1 .5 times the polymer surface energy.

[00010] Embodiment 4 is the method of any of the preceding Embodiments, wherein the support substrate particles have a surface energy of at least 60 dyne/cm.

[00011 ] Embodiment 5 is the method of any of the preceding Embodiments, wherein more than 95 wt.% of the catalyst coating is deposited on the support substrate particle, based on a total amount of the catalyst coating applied to the porous composite.

[00012] Embodiment 6 is the method of any of the preceding Embodiments, wherein the catalyst coating has a loading range of from 0.01% to 40 wt.% based on a total amount of the catalyst coating applied to the porous composite. [00013] Embodiment 7 is the method of any of the preceding Embodiments, wherein the catalyst coated composite is porous.

[00014] Embodiment 8 is the method of any of the preceding Embodiments, wherein the catalyst coated composite is characterized by a catalyst coating gradient (through the Z-axis).

[00015] Embodiment 9 is the method of any of the preceding Embodiments, wherein the catalyst coating includes a high-loading catalyst; wherein more than 10 wt.% of the catalyst coating is deposited on the support substrate particle, based on a total amount of the catalyst coating applied to the porous composite.

[00016] Embodiment 10 is the method of any of the preceding Embodiments, wherein the catalyst coating includes a low-loading catalyst; wherein less than 2 wt.% of the catalyst coating is deposited on the support substrate particle, based on a total amount of the catalyst coating applied to the porous composite.

[00017] Embodiment 11 is the method of any of the preceding Embodiments, wherein the ratio of the catalyst coating deposited on the support substrate to the catalyst coating deposited on a surface of the porous fibri Hated polymer matrix is from 1000:1 to 1.1 :1.

[00018] Embodiment 12 is the method of any of the preceding Embodiments, wherein the support substrate particles are porous or nonporous.

[00019] Embodiment 13 is the method of any of the preceding Embodiments, wherein the support substrate particles have a surface area of from 10 to 5000 m²/g.

[00020] Embodiment 14 is the method of any of the preceding Embodiments, wherein the support substrate particles comprise a metal oxide, silica, clays, diatomaceous earth, zeolites, carbon, activated carbon, or any combination thereof.

[00021] Embodiment 15 is the method of Embodiment 14, wherein the metal oxide includes AI2O3 or TiO2.

[00022] Embodiment 16 is the method of Embodiment 14, wherein the diatomaceous earth includes kieselguhr.

[00023] Embodiment 17 is the method of Embodiment 14, wherein the zeolites comprise X, Y, A, or Zeolite Socony Mobil (ZSM).

[00024] Embodiment 18 is the method of any of the preceding Embodiments, wherein the catalyst coating is applied to the support substrate particles by wet impregnation, coating, imbibing, chemical vapor deposition, atomic layer deposition (ALD), or any combination thereof. [00025] Embodiment 19 is the method of Embodiment 18, wherein the catalyst coating is applied to the porous composite by ALD.

[00026] Embodiment 20 is the method of any of the preceding Embodiments, wherein the catalyst coating includes a platinum family catalyst, a non-platinum family catalyst, metal oxides, ionic liquids, or any combination thereof.

[00027] Embodiment 21 is the method of any of the preceding Embodiments, wherein the porous fibrillated polymer matrix includes an expanded polytetrafluoroethylene or an ultra-high molecular weight polyethylene.

[00028] Embodiment 22 is the method of any of the preceding Embodiments, wherein the catalyst coating is applied at a temperature from 10°C to 250°C.

[00029] Embodiment 23 is the method of Embodiment 22, wherein the applied catalyst coating is subsequently subjected to a heat treatment.

[00030] Embodiment 24 is the method of any of the preceding Embodiments, further including preparing a catalytic article including the porous composite and the catalyst coating.

[00031 ] Embodiment 25 is the method of any of the preceding Embodiments, wherein the catalyst coating is applied to the porous composite using a batch process, a continuous process, or a roll-to-roll process.

[00032] Embodiment 26 is the method of any of the preceding Embodiments, wherein the providing the porous composite includes coating the porous fibrillated polymer matrix with the plurality of support substrate particles using ALD.

[00033] Embodiment 27 is the method of any of the preceding Embodiments, further including applying an additional coating to the catalyst coating; wherein the additional coating may be a promoter coating or a protective coating.

[00034] Embodiment 28 is the method of Embodiment 27, wherein the additional coating is applied to the catalyst coating by ALD.

[00035] According to Embodiment 29, the disclosure provides a catalytic article including: a porous composite including a plurality of support substrate particles non- covalently enmeshed within a porous fibrillated polymer matrix; and a catalyst coating deposited on the support substrate particles, whereby a catalytic article is formed, wherein the catalytic article is characterized by a catalyst coating gradient through the Z-axis. [00036] Embodiment 30 is the catalytic article of Embodiment 29, wherein the porous fibrillated polymer matrix includes a polymer having a surface energy of less than 35 dyne/cm.

[00037] Embodiment 31 is the catalytic article of Embodiment 29 or 30, wherein the support substrate particles have a surface energy that is at least 1 .5 times the polymer surface energy.

[00038] Embodiment 32 is the catalytic article of Embodiments 29 to 31 , wherein the support substrate particles have a surface energy of at least 60 dyne/cm.

[00039] Embodiment 33 is the catalytic article of Embodiments 29 to 32, wherein more than 95 wt.% of the catalyst coating is deposited on the support substrate particle, based on a total amount of the catalyst coating applied to the porous composite.

[00040] Embodiment 34 is the catalytic article of Embodiments 29 to 33, wherein the catalytic article is porous.

[00041 ] Embodiment 35 is the catalytic article of Embodiments 29 to 34, wherein the catalyst coating forms a gradient around the plurality of support substrate particles.

[00042] Embodiment 36 is the catalytic article of Embodiment 35, wherein the gradient is formed from an outer surface of the catalyst coating to an interior surface of the porous composite.

[00043] Embodiment 37 is the catalytic article of Embodiments 29 to 36, wherein the catalyst coating has a thickness of from 0.01 nm to 1 pm as measured from the outer surface of the catalyst coating to the surface of the support substrate particles.

[00044] Embodiment 38 is the catalytic article of Embodiments 29 to 37, wherein the catalyst coating has a depth of from 0.1 nm up to 100% of the thickness of the porous composite as measured from the surface of the support substrate particles to the interior surface of the porous composite.

[00045] Embodiment 39 is the catalytic article of Embodiments 29 to 38, wherein the catalyst coating includes a platinum family catalyst, a non-platinum family catalyst, metal oxides, ionic liquids, or a combination thereof. [00046] Embodiment 40 is the catalytic article of Embodiments s 29 to 39, wherein the catalytic article includes less than 25 wt.% of the catalyst coating based on a total amount of the catalyst coating applied to the porous composite.

[00047] Embodiment 41 is the catalytic article of Embodiments 29 to 40, wherein the porous composite has a porosity of from 5% to 95 % prior to application of the catalyst coating.

[00048] Embodiment 42 is the catalytic article of Embodiments 29 to 41 wherein the catalytic article has a porosity of at least 50%.

[00049] Embodiment 43 is the catalytic article of Embodiments 29 to 43, wherein the porous composite has a surface area of from 50 to 5000 m²/g.

[00050] According to Embodiment 44, the disclosure provides a method including: providing a porous composite including: a plurality of support substrate particles non-covalently enmeshed within a porous fibrillated polymer matrix; and a plurality of heterogeneous catalyst particles substantially deposited on the support substrate particles to form a catalyst coating; and applying an additional coating to the porous composite such that the additional coating is deposited on the catalyst coating.

[00051] Embodiment 45 is the method of Embodiment 44, wherein the additional coating is a promoter coating or a protective coating.

[00052] Embodiment 46 is a process to catalytically convert a reactant to a product including: providing a fluid matrix including the substrate; contacting under suitable reaction conditions the fluid matrix with the catalytic article of Embodiments 29 to 43; whereby the reactant is converted to a product by the catalytic article; and optionally recovering the product from the fluid matrix.

[00053] Embodiment 47 is the process Embodiment 46, wherein the fluid matrix is a liquid, gas, or combination thereof.

[00054] Embodiment 48 is the process Embodiments 46 to 47 wherein the fluid matrix is aqueous or non-aqueous.

[00055] Embodiment 49 is the process Embodiments 46 to 48 wherein the process is a batch process or a continuous process.

[00056] The foregoing Examples are just that and should not be read to limit or otherwise narrow the scope of any of the inventive concepts otherwise provided by the instant disclosure. While multiple examples are disclosed, still other embodiments will become apparent to those skilled in the art from the following detailed description, which shows and describes illustrative examples. Accordingly, the drawings and detailed description are to be regarded as illustrative in nature rather than restrictive in nature.

BRIEF DESCRIPTION OF THE DRAWINGS

[00057] The accompanying drawings are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments, and together with the description serve to explain the principles of the disclosure.

[00058] FIGs. 1 A and 1 B are surface SEM images of alumina-PTFE composite substrates. Figure 1A is a surface SEM image of the alumina-PTFE composite substrate (“Substrate 1A”). Figure 1 B is a surface SEM image of the alumina-PTFE composite substrate (“Support 2C”).

[00059] FIGs. 2A and 2B are SEM images of the composites including y- alumina particles enmeshed with a fibrillated PTFE binder matrix. Fig. 2A is the SEM image before thermal Pd ALD coating (i.e., 0 cycles). Fig. 2B is the composite after 400 cycles of thermal Pd ALD coating.

[00060] FIG. 3 is a cross-section SEM/EDS elemental mapping image of the Y-alumina-PTFE composites after 400 cycles of thermal Pd ALD coating.

[00061] FIG. 4 is an SEM image of 20 wt.% NiO/ALOs-PTFE composite sample showed well disperse nickel particles on the alumina particles and not the PTFE matrix.

DETAILED DESCRIPTION

Definitions and Terminology

[00062] This disclosure is not meant to be read in a restrictive manner. For example, the terminology used in the application should be read broadly in the context of the meaning those in the field would attribute such terminology.

[00063] With respect to terminology of inexactitude, the terms “about” and “approximately” may be used, interchangeably, to refer to a measurement that includes the stated measurement and that also includes any measurements that are reasonably close to the stated measurement. Measurements that are reasonably close to the stated measurement deviate from the stated measurement by a reasonably small amount as understood and readily ascertained by individuals having ordinary skill in the relevant arts. Such deviations may be attributable to measurement error, differences in measurement and/or manufacturing equipment calibration, human error in reading and/or setting measurements, minor adjustments made to optimize performance and/or structural parameters in view of differences in measurements associated with other components, particular implementation scenarios, imprecise adjustment and/or manipulation of objects by a person or machine, and/or the like, for example. In the event it is determined that individuals having ordinary skill in the relevant arts would not readily ascertain values for such reasonably small differences, the terms “about” and “approximately” can be understood to mean plus or minus 10% of the stated value.

[00064] As used herein, the terms “porous supported catalyst particle” and “supported catalyst particle” may be used interchangeably.

[00065] As used herein, the phrase “durably enmeshed” is meant to describe a supported catalyst particle that is non-covalently immobilized within the fibrillated microstructure of the polymer membrane.

[00066] As used herein, the term “finely divided” is meant to denote catalytic metals that are present in particles or grains that have an average particle size less than ten microns in diameter.

[00067] As used herein, the term “fibri Hating” refers to the ability of the fibrillating polymer to form a node and fibril microstructure.

Description of Various Embodiments

[00068] Persons skilled in the art will readily appreciate that various aspects of the present disclosure can be realized by any number of methods and apparatuses configured to perform the intended functions. It should also be noted that the accompanying drawing figures referred to herein are not necessarily drawn to scale but may be exaggerated to illustrate various aspects of the present disclosure, and in that regard, the drawing figures should not be construed as limiting.

[00069] The present disclosure is directed to a porous composite including supported catalyst particles durably enmeshed within a porous polymer matrix, and to methods for forming the composite.

[00070] The catalytic article may include the following:

(i) a porous composite including a plurality of support substrate particles non- covalently enmeshed within a porous fibrillated polymer matrix; and (ii) a catalyst coating deposited on the support substrate particles, whereby a catalytic article is formed, wherein the catalytic article is characterized by a catalyst coating gradient through the Z-axis.

[00071] A method to prepare a catalyst coated composite may include the following steps:

(i) providing a porous composite including a plurality of support substrate particles non-covalently enmeshed within a porous fibrillated polymer matrix; and

(ii) applying a catalyst coating to the porous composite such that the catalyst coating is selectively deposited substantially on the support substrate particles; whereby a catalyst coated composite is formed.

[00072] In some embodiments, the method may include:

(i) providing a porous composite including: a plurality of support substrate particles non-covalently enmeshed within a porous fibrillated polymer matrix; and a plurality of heterogeneous catalyst particles substantially deposited on the support substrate particles to form a catalyst coating; and

(ii) applying an additional coating to the porous composite such that the additional coating is deposited on the catalyst coating.

[00073] In some embodiments, the porous fibrillated polymer matrix may include polytetrafluoroethylene (PTFE), expanded polytetrafluoroethylene (ePTFE), modified PTFE, or a PTFE copolymer. The catalyst coated composite, and the support substrate particles may either alternatively be non-porous or substantially non-porous.

[00074] The supported catalyst particles are formed of at least one finely divided catalytic metal that is supported on and/or within a support substrate. In some embodiments, the finely divided catalytic metal has a range from about 0.1 nm to about 50 nm. Catalytic metals suitable for incorporation onto the support substrate include elements selected from Group Vb, Group Vlb, Group VI lb, Group VII lb, and Group lb metals of the periodic table. The catalyst coating may also include a platinum family catalyst, such as platinum, palladium, rhodium, iridium, ruthenium, or osmium. The catalyst coating may include a non-platinum family catalyst such as cobalt, nickel, copper, zinc, iron, molybdenum, vanadium, chromium, or manganese. Raney-type metals or sponge nickel may also be used. Metal oxides or ionic liquids of any of the foregoing metals may be also used as catalysts.

[00075] In some embodiments, mixtures of catalytic metals (e.g., palladium and nickel or copper chromium oxides) are dispersed onto the support substrate.

[00076] In some embodiments, the finely divided metal catalysts may be dispersed onto and/or into the support substrate by known and optimized processes described in the art including, but not limited to, precipitation, plating, atomic layer deposition, wet impregnation, coating, imbibing, chemical vapor deposition, and molecular layer depositions. Incipient wetness from a salt solution of the catalytic metal is one non-limiting example of a method for incorporating a catalytic metal on the substrate particle.

[00077] In alternative embodiments, the catalyst coatings may be applied at a temperature of as low as 5°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, or as high as 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, or within any range encompassed by any two of the foregoing values as endpoints. For example, the catalyst coating may be applied at a temperature of from 10°C to 250°C.

[00078] After being applied, the catalyst coating may be subsequently subjected to a heat treatment. The catalyst coating may be applied to the porous composite using a batch process, a continuous process, or a rol l-to-rol I process.

[00079] In some embodiments, the catalyst coatings may be deposited onto the support substrate particle in an amount of more than 70%, more than 75%, more than 80%, more than 85%, more than 90% more than 95%, more than 96%, more than 97%, more than 98%, more than 99%, or within any range encompassed by any two of the foregoing values as endpoints based on a total amount of the catalyst coating applied to the porous composite.

[00080] In some embodiments, the catalyst coating may have a loading range of as low as 0.001 %, 0.01 %, 0.05%, 0.1 %, 0.5%, 1 %, 2%, 3%, or as high as 4%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, or within any range encompassed by any two of the foregoing values as endpoints, based on a total amount of the catalyst coating applied to the porous composite. For example, the catalyst coating may have a loading range of from 0.01 % to 40%.

[00081] In certain embodiments, the catalyst coating may include a high- loading catalyst, wherein more than 10 wt.% of the catalyst coating is deposited on io the support substrate particle, based on a total amount of the catalyst coating applied to the porous composite. As used herein, a “high-loading catalyst” refers to a catalyst with more than 10% deposited on the substrate support particle.

[00082] In some embodiments, the catalyst coating may include a low-loading catalyst, wherein less than 2 wt.% of the catalyst coating is deposited on the support substrate particle, based on a total amount of the catalyst coating applied to the porous composite. As used herein, a “low-loading catalyst” refers to a catalyst with less than 2 wt% deposited on the substrate support particle.

[00083] In some embodiments, the ratio of the catalyst coating deposited on the support substrate to the catalyst coating deposited on a surface of the porous fibrillated polymer matrix may be as high as 1.1 :1 , 2:1 , 3:1 , 4:1 , 5:1 , 6:1 , 7:1 , 8:1 , 9:1 , 10:1 , 25:1 , 50:1 , 90:1 , or at least 99:1 or within any range encompassed by any two of the foregoing values as endpoints.

[00084] In some embodiments, the catalyst coating may have a thickness of about 0.01 nm, 0.1 nm, 0.5 nm, 1 nm, 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, or as high as 11 nm, 12 nm, 13 nm, 14 nm, 15 nm, 16 nm, 17 nm, 18 nm, 19 nm, 20 nm, 50 nm, 100 nm, 500 nm, 1 pm or within any range encompassed by any two of the foregoing values as endpoints, as measured from the outer surface of the catalyst coating to the surface of the support substrate particles. For example, the catalyst coating may have a thickness of from 0.01 nm to 1 pm.

[00085] In some embodiments, the catalyst coating may penetrate partially or fully through the porous composite.

[00086] The catalyst coated composite as described herein may have a catalyst coating gradient through either the X, Y, or Z axis. In one embodiment, the catalyst coated composite has a catalyst coating gradient in the Z-axis (i.e. , thickness). For example, the catalyst coating gradient may have a relative catalyst content (wt%) through the Z-axis (a catalyst coating thickness gradient through the thickness of the catalyst coated composite where the catalyst coated composite has a higher wt% of the catalyst coating on one side of the catalyst coated composite and a decreasing wt% of the catalyst coating through the Z-axis to the opposing side) of the catalyst coated composite of 10:1 , 5: 1 ,3:1 , 2:1 , 1.1 :1 or 1 :10, 1 :5, 3:1 , 1 :2 or 1 :1.1.

[00087] High catalytic activity is gained by the effective fine dispersion of the finely divided metal catalyst such that the metal catalyst covers the support substrate ii and/or is interspersed in the pores of the support substrate.

[00088] An additional coating may be applied to the catalyst coating such as a promoter coating or a protective coating. The promoter or protective coating may be a coating such as ZnO, TiO2, CeO2, SiC>2, HfO2, AI2O3 or any combination thereof. The additional coating may be applied by known and optimized processes described in the art including, but not limited to, precipitation, plating, atomic layer deposition, wet impregnation, coating, imbibing, chemical vapor deposition, and molecular layer depositions.

[00089] The support substrate is not particularly limiting so long as it does not affect the multiphase catalytic reaction in which it is used. In exemplary embodiments, the support substrate is porous. Examples of materials for use as the support substrate include, but are not limited to, metals, metal oxides (e.g., aluminum oxide (AI2O3) or titanium oxide (TiC )), silica, clays, diatomaceous earth (e.g., kieselguhr), zeolites (e.g., X, Y, A, and Zeolite Socony Mobil (ZSM)), carbon, and activated carbon, or any combination thereof. In at least one embodiment, the support substrate is generally spherical or semispherical in shape and has a diameter in the range from about 100 nm to 500 pm, 150 nm - 200 pm, 5 pm - 200 pm . It is to be appreciated that the term support substrate is not meant to be limiting, and particles, flakes, fibers, nanotubes, nanoparticles, platelets, and powders are considered to be within the purview of the present disclosure.

[00090] In certain embodiments, the support substrate particles may have a surface energy that is at least 1 .5 times the surface energy of the fibril lated polymer matrix. In other words, the support substrate particles may have a surface energy as low as 25 dyne/cm, 30 dyne/cm, 35 dyne/cm, 40 dyne/cm, 45 dyne/cm, 50 dyne/cm, or as high as 55 dyne/cm, 60 dyne/cm, 65 dyne/cm, 70 dyne/cm, 75 dyne/cm, 80 dyne/cm, 85 dyne/cm, 95 dyne/cm, 100 dyne/cm, or within any range encompassed by any two of the foregoing values as endpoints.

[00091 ] In some embodiments, the support substrate particles may have a surface area of as low as 10 m²/g, 15 m²/g, 20 m²/g, 25 m²/g, 30 m²/g, 35 m²/g, 40 m²/g, or as high as 45 m²/g, 50 m²/g, 55 m²/g, 60 m²/g, 65 m²/g, 70 m²/g, 75 m²/g, 80 m²/g, 100 m²/g, 250 m²/g, 500 m²/g, 1000 m²/g, 5000 m²/g or within any range encompassed by any two of the foregoing values as endpoints.

[00092] As discussed above, the supported catalyst particles are durably enmeshed in an expanded polymer matrix. No separate binder is present to fix the supported catalyst particles in the membrane. Additionally, the supported catalyst particle is located throughout the thickness of the fibrillated polymer matrix. The porous nature of the fibrillated polymer matrix allows free access to the supported catalyst particles (solid phase) by the liquid/gas mixture (liquid/gas phase). The average pore size may range from about 3 nm to about 950 pm as determined by mercury porosimetry.

[00093] The polymer forming the fibrillated polymer matrix is a solvent inert or solvent resistant polymer. In particular, the polymer may be both insoluble and inert to the reactants and products of the multiphase chemical reaction in which it is used. The fibrillated polymer matrix may include polytetrafluoroethylene (PTFE), expanded polytetrafluoroethylene (ePTFE), poly(ethylene-co-tetrafluoroethylene) (ETFE), ultra- high molecular weight polyethylene (UHMWPE), polyethylene, poly(para-xylylene) (PPX), polylactic acid (PLLA), polyethylene (PE), expanded polyethylene (ePE), and any combination or blend thereof. It is to be understood that throughout this disclosure, the term “PTFE” is meant to include not only polytetrafluoroethylene, but also expanded PTFE, modified PTFE, expanded modified PTFE, and expanded copolymers of PTFE. The porous fibrillated polymer matrix may also be formed of one or more monomers of tetrafluoroethylene, ethylene, p-xylene, and lactic acid. In at least one embodiment, the porous fibrillated polymer matrix is included of solvent inert sub-micron fibers of an expanded fluoropolymer.

[00094] In some embodiments, the fibrillated polymer matrix may include a polymer with a surface energy of less than 50 dyne/cm, less than 45 dyne/cm, less than 40 dyne/cm, less than 35 dyne/cm, less than 30 dyne/cm, less than 25 dyne/cm, less than 20 dyne/cm or within any range encompassed by any two of the foregoing values as endpoints.

[00095] In some embodiments, the fibrillated polymer matrix is a polytetrafluoroethylene (PTFE) membrane or an expanded polytetrafluoroethylene (ePTFE) membrane having a node and fibril microstructure. The fibrils of the PTFE particles interconnect with other PTFE fibrils and/or to nodes to form a net within and around the supported catalyst particles, effectively immobilizing them. Therefore, in one non-limiting embodiment, the fibrillated polymer matrix may be formed of a network of PTFE fibrils immobilizing and enmeshing the supported catalyst particles within the fibrillated microstructure.

[00096] The porous fibrillated polymer matrix may be formed by blending fibrillating polymer particles with the supported catalyst particles followed by uniaxial or biaxial expansion. The mixing may be accomplished, for example, by wet or dry mixing, by dispersion, or by coagulation. Time and temperatures at which the mixing occurs varies with particle size, material used, number of particles being co-mixed, etc. and are easily identified by those of skill in the art. The uniaxial or biaxial expansion may be in a continuous or batch processes.

[00097] In some embodiments, the catalytic article may include less than 40 wt.%, less than 35 wt.%, less than 30 wt.%, less than 25 wt.%, less than 20 wt.%, less than 15 wt.%, less than 10 wt.%, less than 5 wt.%, or within any range encompassed by any two of the foregoing values as endpoints of the catalyst coating based on a total amount of the catalyst coating applied to the porous composite.

[00098] In some embodiments, the porous composite included within the catalytic article may have a porosity of as low as 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or as high as 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or within any range encompassed by any two of the foregoing values as endpoints. For example, the porous composite may have a porosity of from 5% to 95%, or at least 50%.

[00099] In some embodiments, the porous composite included within the catalytic article may have a surface area of as low as 50 m²/g, 55 m²/g, 60 m²/g, 65 m²/g, 70 m²/g, 75 m²/g, 80 m²/g, 85 m²/g, 90 m²/g, 95 m²/g, 100 m²/g, 105 m²/g, 110 m²/g, 115 m²/g, 120 m²/g, 125 m²/g, 130 m²/g, 135 m²/g, 140 m²/g, 145 m²/g, 150 m²/g, 250 m²/g, 500 m²/g, 1000 m²/g, 5000 m²/g or within any range encompassed by any two of the foregoing values as endpoints. For example, the porous composite may have a surface area of from 50 to 5000 m²/g.

[000100] Also disclosed herein is a process for catalytically converting a substrate to a product using the catalytic article of the present disclosure. The process may include the following steps:

(i) providing a fluid matrix including a reactant;

(ii) contacting under suitable reaction conditions the fluid matrix with the catalytic article of any of claims 29 to 43; whereby the reactant is converted to a product by the catalytic article; and

(iii) optionally recovering the product from the fluid matrix.

[000101] The fluid matrix may be a liquid, gas, or any combination thereof. The fluid matrix may be aqueous or non-aqueous. [000102] The process may be done in batches or as a continuous process.

TEST METHODS

[000103] It should be understood that although certain methods and equipment are described below, other methods or equipment determined suitable by one of ordinary skill in the art may be alternatively utilized.

Mercury Porosimetry Testing

[000104] Porosity measurements may be conducted on a Micromeritics AutoPore V mercury porosimeter (Micromeritics, Norcross, Ga., USA), using Micromeritics MicroActive software version 2.0. Quadruple Distilled Virgin Mercury - 99.9995% purity (Bethlehem Apparatus, Bethlehem, PA) is used as received for tests. Tests may use a solid type of penetrometer with a bulb volume of 5 cc and a stem volume of 0.392 cc (SN: 07-0979). Pieces of the composite samples are cut into 1 cm X 2 cm strips and enough of these strips are weighed on an analytical balance to provide a total mass of approximately 0.25 g. After noting the mass, the sample pieces are placed in the penetrometer.

[000105] The test parameters may be as follows: (1 ) the penetrometer is placed into the low pressure port on the AutoPore and evacuated to 50 pm Hg, followed by 5 min unrestricted evacuation; (2) the penetrometer is then filled with mercury at 0.5 psia (~3.5 kPa) and equilibrated for 10 seconds; pressure is subsequently applied to the capillary using nitrogen in steps up to 30 psia (~0.21 MPa), equilibrating for 10 seconds at each step prior to determining the intrusion volume via the standard capacitance measurement with the penetrometer capillary; (3) the penetrometer is then removed from the low pressure port after returning to atmospheric pressure and then weighed to determine the amount of mercury added; (4) the penetrometer is subsequently placed into the high pressure port on the AutoPore and the pressure is again increased in a series of steps up to approximately 60,000 psia (~ 413.7 MPa) allowing 10 sec at each step to equilibrate prior to intrusion volume measurements.

[000106] The intrusion volume V at any pressure is determined through a capacitance measurement using the pre-calibrated capillary (i.e., a cylindrical capacitor where the outer contact is the metallized coating on the external surface of the glass capillary, the inner contact is the liquid mercury, and the dielectric is the glass capillary). The total intrusion volume divided by the sample mass gives the specific intrusion volume (in mL/g).

[000107] The volume occupied by the sample is then calculated at the two extreme target pressures, namely, 0.5 psia (~3.5 kPa) and 60,000 psia (~ 413.7 MPa). Since the penetrometer has a known calibrated volume, the difference between this volume and the mercury volume (determined from the mass increase after mercury addition at low pressure and the density of mercury) yields the volume of the sample including any pores. Dividing the mass of the sample by the volume at this low pressure provides the bulk density of the sample. At high pressure, where mercury has been pushed into the pores by an amount given by the intrusion volume, the skeletal density can be approximated by dividing the sample mass by the adjusted sample volume (e.g., low pressure volume minus total intrusion volume).

Total Pore Area

[000108] The total pore area reported is determined through a series of intermediate calculations. First, the diameter of the pores being filled at a given pressure is calculated using the Washburn equation:

[000109] where D, = pore diameter at the i^th pressure point, y = surface tension, 0 = contact angle and B = pressure. The mean diameter for the i^th point is then taken to be:

Drrii = (Di +D ) / 2

[000110] The incremental specific intrusion volume for the i^th point is calculated from the total intrusion volume taken at each point (li): lii = li - I [000111] Finally, the incremental specific pore area for the i^th point is calculated from the incremental intrusion volume and the mean diameter from:

Aii = (4 X lii) / Dmi

[000112] The total (i.e. , cumulative) specific pore area for the i^th point is then calculated as:

Ai = Aii + Aii-i + ... +Aii.

Bulk Density

[000113] The bulk density of the sample is the density of the solid including all open pores and internal void volume. The bulk density is calculated by dividing the sample mass by the low-pressure mercury intrusion volume. Sample mass is determined by weighing on an analytical balance of +/- 0.01 mg sensitivity.

Bulk Density — M/(Vl_ow Pressure)

Skeletal Density

[000114] The skeletal density is the density of a solid calculated by excluding all open pores and internal void volume. The skeletal density is calculated by dividing the sample mass by the adjusted sample volume (low pressure volume minus total intrusion volume). The sample mass is determined by weighing on an analytical balance of +/- 0.01 mg sensitivity.

Skeletal Density ⁼ M/((Vl_ow Pressure) — (VHigh Pressure))

[000115] where VLOW Pressure is volume of the sample at 0.5 psia (~3.5 kPa) and VHigh Pressure is total intrusion volume at 60,000 psia (~ 413.7 MPa).

Total Porosity

[000116] The total porosity within the substrate is simply the void volume of the sample divided by the total volume of the sample. This was calculated as: %Porosity = 100 * (total intrusion volume at 60,000 psia (~ 413.7 MPa))/(volume of the sample at 0.5 psia (~3.5 kPa)).

Thickness

[000117] Sample thickness was measured by placing the sample (e.g., composite membrane) between the two plates of a Kafer FZ1000/30 thickness snap gauge (Kafer Messuhrenfabrik GmbH, Villingen-Schwenningen, Germany). The average of the three measurements was used.

Scanning Electron Micrographs (SEM)

[000118] The SEM samples were imaged at 1 .0 to 10 kV using a Hitachi FlexSEM 1000 II (Hitachi High-Tech America, Inc., Schaumburg, IL). Samples were coated with a thin layer of platinum prior to analysis with a Cressington 208HR sputter coater (Cressington Scientific Instruments Ltd., Watford, UK).

SEM/EDS elemental mapping

[000119] Energy-dispersive spectroscopy (EDS) was performed on an Oxford X-Max detector running AZtec® software using the default setting provided by the manufacturer unless otherwise noted (Oxford Instruments Pic, Oxfordshire, UK) Spectroscopic Ellipsometry

[000120] Ellipsometry is an optical technique for investigating the dielectric properties (complex refractive index or dielectric function) of thin films. Ellipsometry measures the change of polarization upon reflection or transmission and compares it to a model. “Handbook of Ellipsometry" by Harland Tompkins and Eugene A Irene, Published by William Andrew Publishing, Norwich, NY, (2005). A Sentech SE400adv laser ellipsometer (SENTECH Instruments GmbH, Berlin, Germany) using wavelength 633 nm and measuring angle 70°. Although the method is not ideal for non-transparent materials, thin layers (< 10 nm) can be measured with fairly good reliability. The refractive index was fixed at 1 ,7703 and only Pd layer thickness was modelled.

X-ray photoelectron spectroscopy (XPS) [000121 ] X-ray photoelectron spectroscopy (XPS) is a surface-sensitive quantitative spectroscopic technique based on the photoelectric effect that can identify the elements that exist within a material (elemental composition) or are covering its surface, as well as their chemical state, and the overall electronic structure and density of the electronic states in the material (see Moulder, J.F. et al., Handbook of X-Ray Photoelectron Spectroscopy: A Reference Book of Standard Spectra for Identification and Interpretation of XPS Data, Perkin-Elmer, Eden Prairie, Minn, USA, 1992). XPS survey scans were run on 5 areas to quantify the surface composition. High-resolution X-ray photoelectron spectroscopy (HR-XPS) spectra of palladium region were used to determine the palladium chemical state.

Carbon Monoxide (CO) Chemisorption

[000122] CO chemisorption was used to evaluate the number of available active sites for the Pd catalyst prepared by ALD. Samples between 0.1 and 0.5 g were used for the analysis and the palladium weight percent (wt.%) determined by ICP was used for the calculations. Samples were loaded into a U-shaped quartz tube flow cell holder (Quantachrome by Antonn Paar). The inlet diameter of the cell is 12 mm. The exit side of the cell has a capillary bore. A small quantities of quartz wool is placed at the bottom of the tube to prevent elutriation of sample to the capillary. The sample is then added to the cell followed by another small amount of quartz wool and a filler quartz tube rod that reduces the void volume of the inlet section. The samples were heated to 200 °C with heating rate of 10 °C/min, under He flow. Flow of He was continued for 120 min at that temperature. Then the sample was reduced for 600 min at 200 °C under 99.999% H2 flow. Once reduction step was completed, the samples were purged with He for 120 min at 200 °C. Then they were cooled down to 40 °C under He flow and were further purged with He for 30 min before the CO pulse titration sequence. In the pulse titration experiment an inert gas (He) is flow over the sample at constant temperature (40 °C) and successive doses of a known volume of a reactive gas (approximately 18 mL of CO) are injected into the stream before the sample. The residual amounts of CO past the sample were monitored via a TCD detector. When all the gas forms each dose passes through the sample then is assumed that the active sites are saturated. The amount adsorbed is calculated from the amount of each injection minus the amount detected at the outlet. To calculate Pd surface area it is assumed that each CO molecule reacts with one Pd site and that the cross-sectional area of each site is 7.874 Angstrom per atom.

Inductively Coupled Plasma (ICP) Metal Analysis

[000123] Inductively coupled plasma optical emission spectroscopy (ICP-OES) was conducted by Robertson Microlit Laboratories (Ledgewood, NJ.) in compliance with United States Pharmacopeia (USP) Chapters <730>/<1730>, Chapters <232>/<233>, and the International Council for Harmonisation (ICH) Guideline for Elemental Impurities Q3D (US FDA, Rockville, MD)

Brunauer, Emmett and Teller (BET) Theory Gas Sorption Analysis

[000124] BET analysis was performed on a Quantachrome NOVA 1200e gas sorption instrument (Anton Paar GmbH, Graz, Austria) using nitrogen as adsorbate at 77 K. All samples were degassed at 100 °C overnight under vacuum. Surface area calculations were performed using BET theory (S. Brunauer et al., J. Amer. Chem. Soc., 60:309 (1938); ). The collection of adsorption data points used in the BET calculation were selected using the criteria suggested by Rouquerol (Rouquerol et al., Stud Surf Sci Catal. (2006); 160:49-56). The BET equation yielded linear relationships, the summary of resulting data from the BET analysis and isotherms are in Table 4.

[000125] BET analysis was performed on a Quantachrome NOVA 1200e gas sorption instrument. International Organization for Standardization (ISO 9277:2010 “Determination of the specific surface area of solids by gas adsorption — BET method”)

[000126] S. Brunauer, P.H. Emmett, E. Teller, J. Amer. Chem. Soc., 60:309 (1938).

Temperature programmed reduction (TPR)

[000127] Temperature programmed reduction (TPR) was used to determine the reduction temperature of the nickel sample. Approximately 0.4 grams of sample were loaded into a U-shaped quartz tube flow cell holder (Quantachrome by Antonn Paar). The inlet diameter of the cell is 12 mm. The exit side of the cell has a capillary bore. A small quantities of quartz wool is placed at the bottom of the tube to prevent elutriation of sample to the capillary. The sample is then added to the cell followed by another small amount of quartz wool and a filler quartz tube rod that reduces the void volume of the inlet section. The sample was heated to 275 °C with a heating rate of 20 °C/min under He flow (approximately 50 cc/min). Flow of He was continued for 120 min at that temperature. The sample was then cooled to 60 °C under He flow. Once temperature stabilized, the flow was switched to 3.8% H2/N2 for 35 min at 60 °C. Then the temperature was increased to 275 °C with a ramp rate of 1 .5 °C/min under 3.8% H2/N2 flow. The TCD and MS were recorded during the heat ramp.

Thermal Atomic Laver Deposition (ALP)

[000128] Thermal atomic layer deposition of palladium (Pd) on gamma-alumina (y-alumina) particles enmeshed and immobilized within a fibrillated polymer binder matrix was demonstrated. Depositions were conducted in Beneq TFS 200 reactor (Beneq Inc., Espoo, Fl) at deposition temperature of 200 °C. Three different deposition processes were initially evaluated. The process producing film with best electrical conductivity was chosen. A series of test depositions with varying number of cycles was conducted to determine the growth per cycle (GPC). Finally, four sample depositions with 50, 100, 200 and 400 Pd ALD cycles were conducted on gammaalumina particle-filled PTFE composites as substrates. According to ellipsometry, GPC for sample depositions was approximately 0.09-0.14 A/cycle. The Pd was deposited selectively in the support particles of the particles filled PTFE composites.

EXAMPLES

[000129] Unless defined otherwise herein, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The present invention is further defined in the following Examples. It should be understood that these Examples, while indicating preferred embodiments of the invention, are given by way of illustration only. From the above discussion and these Examples, one skilled in the art can ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various uses and conditions.

I: Preparation of a Porous Composite (“Substrate 1A") Including v-Alumina Particles Enmeshed and Immobilized with a Fibrillated Polymer Matrix

[000130] A composite of blend of 23 wt.% polytetrafluoroethylene (PTFE) fine particles and 77 wt.% Type 26R-0842UPGG gamma-alumina (y-alumina) from Inframat Advanced Materials, LLC (Manchester, CT, USA) having an average particle size of approximately 40 pm was blended with sufficient sheer to induce fibrillation of the PTFE particles in a manner generally taught in United States Publication No. 2005/0057888 to Mitchell et al. The resulting porous PTFE composite included the y-alumina support particles enmeshed and immobilized within the fibrillated PTFE matrix (i.e. , a microstructure of nodes interconnected by fibrils). The Substrate 1 A had a thickness of 0.55 mm. The substrate was characterized by mercury porosimetry to have a total porosity of 63.6%, a bulk density of 1.17 g/cm³, and a skeletal density of 3.21 g/cm³ Scanning electron microscopy (SEM) analysis was on Substrate 1 A (Fig. 1 A). Properties of the y- alumina particles and the resulting porous composite are provided in Table 1.

[000131 ] Circular samples (85 mm in diameter) were cut were cut from the porous PTFE composite tape and mounted in a custom metal sample holder for thermal ALD deposition.

[000132] Figure 1a shows surface SEM image of the alumina-PTFE substrate. Table 1 summarizes properties of the y-alumina particles and y-alumina particle-filled PTFE composites.

Alumina-PTFE composite as substrate for Thermal Pd Atomic Layer Deposition [000133] Depositions were conducted using a Beneq TFS 200 ALD reactor (Beneq Inc., Espoo, Fl) at a deposition temperature of 200 °C. Small pieces of silicon wafer with approximately 6 nm ALD-AI2O3 (measured by ellipsometry) were used for the test deposition. Three slightly different processes (A, B and C) were assessed to determine the process for the sample deposition. Process A provided film with best electrical conductivity and was therefore chosen for sample depositions. To determine the growth per cycle (GPC) for the process a series of depositions with varying number of cycles were conducted. Table 2 summarizes the test deposition with number of ALD cycles, Pd thickness and growth per cycle (GPC) data of the process selected for the sample deposition. [000134] Alumina particle-filled PTFE composite substrates were gently blown with nitrogen upon loading into the reactor. For sample depositions, a 200 mm silicon wafer was placed at the bottom of the deposition chamber. Alumina particle-filled PTFE composite sample was lifted up and supported by three sample holders in order to allow uniform precursor gas flow for both sides of the sample substrate. Depositions were conducted in a Beneq TFS 200 reactor (Beneq Inc., supra) at deposition temperature of 200 °C using palladium (ii) hexafluoroacetylacetonate (Pc/(CsHF6O2)2 or Pd(hfac)2) and hydroxymethylene (HCOH). Four samples were prepared varying the ALD number of cycles (50 cycles, 100 cycles, 200 cycles and 400 cycles). After the deposition ended, the reactor was left to cool down slowly in vacuum until the temperature was below 100°C.

[000135] Film thicknesses were measured by laser ellipsometry (Sentech SE400adv laser ellipsometer, SENTECH Instruments GmbH, Berlin, Germany) using wavelength 633 nm and measuring angle 70°. Although the method is not ideal for non-transparent materials, thin layers (< 10 nm) can be measured with fairly good reliability. Refractive index was fixed at 1 ,7703 and only Pd layer thickness was modelled. Table 3 summarizes the data for the sample deposition. The GPC of 0.09 to 0.14 A/cycle for sample depositions were notably higher compared to 0.02 to 0.07 A/cycle for test deposition. The Pd ALD coating on the silicon wafer showed discrete small particles. The coverage of the particles increases as does the particle size (approximately 6 to 8 nm) and then a continuous layer is observed. X-ray photoelectron spectroscopy (XPS) showed an increase in the surface Pd concentration and decrease in the surface Si concentration with the number of ALD cycles.

[000136] An inductively coupled plasma (ICP) analysis was used to determine the metal loading in the samples (see Table 3). The palladium loading in the samples increase from 0.06 wt.% to 1 .15 wt.% with increase in ALD cycles (50 cycles to 400 cycles). The amount of Pd was not linear with coating cycles, where was observed a low increase between 50 ALD cycles to 200 ALD cycles and higher increase between 200 ALD cycles and 400 ALD cycles. Color changes were observed in the samples from white (Substrate 1A) to light gray (Example 1A) to dark gray/black (Example 1 D) which demonstrate the increase in Pd deposition with number of ALD cycles. White areas were observed on the surface of the samples that correspond to areas with PTFE. The selective deposition of the Pd on the support particles was evaluated by SEM images. Also, the coverage of the Pd increases with number of ALD cycles.

[000137] Figure 2 shows SEM images of the y-alumina particle-filled PTFE composites (a) before and (b) after 400 cycles of thermal Pd ALD coating. The alumina particles and PTFE (0 cycles) is shown in Figure 2a. For Examples 1A, the presence of Pd on either the alumina or PTFE is not distinguishable. Examples 1 B to 1 D showed that small discrete Pd particles decorate the surface of the alumina and are not evident on the PTFE. These samples showed well-dispersed Pd particles on the alumina contrary to the silicon wafer that showed Pd particles begin to form a continuous film. Also, higher Pd particle coverage with uniform distribution on alumina were observed at 400 ALD cycles (see Figure 2b). At 200 ALD cycles and 400 ALD cycles, Pd particles are not evident on the PTFE.

[000138] A Pd penetration/deposition gradient can be observed in the samples with number of ALD cycles. Higher Pd penetration was observed with higher number of ALD cycles and where the alumina is in the surface. For 50 ALD cycles, Pd cannot be discerned in the sample cross-section SEM/EDS elemental mapping but the spectrum of surface sample indicates the relative concentration of approximately 0.2 wt.% of Pd. For 100 ALD cycles, the cross-section SEM/EDS elemental mapping shows that the Pd penetration is about 25 microns, and the spectrum of surface sample indicates the relative concentration of approximately 0.7 wt.% of Pd. The gradient of Pd penetration, in both sides, vary in the samples. For 200 ALD cycles, the cross-section SEM/EDS elemental mapping showed approximately 40 microns of Pd penetration, and the spectrum taken from the surface of the sample indicates a relative concentration of approximately 5 wt.% of Pd on the surface. Figure 3 shows SEM/EDS elemental mapping of the y-alumina particle-filled PTFE composites after 400 cycles of thermal Pd ALD coating. Figure 3 shows a gradient of up to 60 microns of Pd penetration and the spectrum taken from the surface of the sample indicates a relative concentration up to 11 wt.% of Pd on the surface.

[000139] X-ray photoelectron spectroscopy (XPS) survey scans were run on 5 areas to quantify the surface composition. High-resolution X-ray photoelectron spectroscopy (HR-XPS) spectra of the palladium region were used to determine the palladium chemical state. HR-XPS of the palladium region were conducted for the y- alumina particle-filled PTFE composites after thermal Pd ALD coating and after sputtering the surface with T Ar at 1 keV. HR-XPS of Pd region is consistent with literature values for palladium II oxide (PdO) at 336.0 eV. Despite this observation, there does not appear to be enough oxygen present to account for aluminum oxide, AI2O3, and PdO. Brief sputter induced a slight shift in the palladium binding energy to slightly lower values of 335.6 eV, which are in the realm of binding energies for metallic Pd.

[000140] CO chemisorption was used to evaluate the number of available active sites for the Pd catalyst prepared by ALD. Samples between 0.1 and 0.5 g were used for the analysis and the palladium weight percent (wt.%) determined by ICP was used for the calculations. Samples were loaded into a U-shaped quartz tube flow cell holder (Quantachrome by Anton Paar). The inlet diameter of the cell was 12 mm. The exit side of the cell has a capillary bore. A small quantity of quartz wool is placed at the bottom of the tube to prevent elutriation of sample to the capillary. The sample is then added to the cell followed by another small amount of quartz wool and a filler quartz tube rod that reduces the void volume of the inlet section. The samples were heated to 200°C with heating rate of 10°C/min, under He flow. Flow of He was continued for 120 min at that temperature. Then the sample was reduced for 600 min at 200°C under 99.999% H2 flow. Once the reduction step was completed, the samples were purged with He for 120 min at 200°C. Then they were cooled down to 40 °C under He flow and were further purged with He for 30 min before the CO pulse titration sequence. In the pulse titration experiment an inert gas (He) was flowed over the sample at constant temperature (40 °C) and successive doses of a known volume of a reactive gas (approximately 18 mL of CO) are injected into the stream before the sample. The residual amounts of CO past the sample were monitored via a TCD detector. When all the gas from each dose passes through the sample then is assumed that the active sites are saturated. The amount adsorbed was calculated from the amount of each injection minus the amount detected at the outlet. To calculate Pd surface area it is assumed that each CO molecule reacts with one Pd site and that the cross-sectional area of each site is 7.874 Angstrom per atom.

[000141 ] Table 3 shows the Pd surface area between 0.07 to 0.26 m² per grams of sample. When normalized by loading, the samples have up to 114 m² per grams of palladium. II. Examples of nickel impregnation

[000142] Impregnation of nickel on y-alumina particle-filled PTFE composites as structured support was demonstrated. The nickel was deposited selectively in the support particles of the particle-filled PTFE composites. Samples of 1 wt.%, 10 wt.%, 20 wt.% and 25 wt.% of nickel were prepared to determine the higher loading with more homogeneous particles and distribution. Finally, two samples with 20 wt.% Ni were prepared on y-alumina particle-filled PTFE composites with different porosities. Nickel particles were deposited selectively in the support particles and through the thickness of both alumina particle-filled PTFE composites.

Support 2A: y-alumina particle-filled PTFE composites

[000143] A composite of blend of 22 wt.% PTFE and 78 wt.% Type 26R- 0842UPGG y-alumina from Inframat Advanced Materials, LLC (supra) having an average particle size of approximately 40 pm was blended in a manner generally taught in United States Publication No. 2005/0057888 to Mitchell, et al. The resulting porous PTFE composite included support particles enmeshed and immobilized within the porous PTFE node and fibril matrix. The Support 2A had a thickness of 0.92 mm. The structured support was characterized by mercury porosimetry to have a total porosity of 57.9%, a bulk density of 1 .58 g/cm³, and a skeletal density of 3.14 g/cm³ The samples were cut in squares of approximately 2x2 mm using a frozen blade.

Support 2B: y-alumina particle-filled PTFE composites

[000144] A composite of blend of 23 wt.% PTFE and 77 wt.% Type 26R- 0842UPGG y-alumina from Inframat Corporation (CT, USA) having a size of approximately 40 pm was blended in a manner generally taught in United States Publication No. 2005/0057888 to Mitchell, et al. The resulting porous PTFE composite included support particles enmeshed and immobilized within the porous PTFE node and fibril matrix. The Support 2C had a thickness of 0.88 mm. The structured support was characterized by mercury porosimetry to have a total porosity of 26.3%, a bulk density of 1 .51 g/cm³, and a skeletal density of 3.07 g/cm³. The samples were cut in squares of approximately 2x2 mm using a frozen blade. Support 2C: y-alumina particle-filled ePTFE composites

[000145] A composite of blend of 23 wt.% PTFE and 77 wt.% Type 26R- 0842UPGG y-alumina from Inframat Corporation (CT, USA) having a size of approximately 40 pm was blended in a manner generally taught in United States Publication No. 2005/0057888 to Mitchell, et al. and subsequently uniaxially expanded according to the teachings of U.S. Pat. No. 3,953,566 to Gore. The resulting porous fibrillated ePTFE composite included support particles enmeshed and immobilized within the ePTFE node and fibril matrix. The porous fibrillated ePTFE composite, Support 2C, had a thickness of 0.58 mm. The structured support was characterized by mercury porosimetry to have a total porosity of 77.8%, a bulk density of 0.81 g/cm³, and a skeletal density of 3.17 g/cm³ The samples were cut in squares of approximately 2x2 mm using a frozen blade.

[000146] Table 1 summarizes properties of the y-alumina particles and y- alumina PTFE composites. Figure 1 b shows surface SEM images of the alumina- ePTFE composite (Support 2C).

Nickel impregnation using gamma-alumina particles filled ePTFE composite as structured support

[000147] Nickel (Ni) depositions were conducted by impregnation of 4 mL nickel (II) nitrate hexahydrate (Ni(NO3)2'6H2O) solution in water/isopropyl alcohol (1 :1 ). Nickel solution was added to approximately 2.4 g of 2x2 mm AI2O3-PTFE until the composites were wet, followed by solvent evaporation at 120 °C. These steps were repeated until all the solution was used and then calcination overnight at 250 °C in air. For comparison, nickel impregnated into the y-Al2O3 powder was prepared similar to above. Samples were prepared with different Ni loadings (1 wt.%, 10 wt.%, 20 wt.% and 25 wt.%) in the alumina particles of the composites. After calcination, color change was observed in the samples to white and light gray (1 wt.%) to dark gray/black (25 wt.%) which demonstrate the nickel deposition. The 1 wt.% sample have areas that look like no Ni deposition was done. Nickel loading by ICP analysis were agreement with the calculated values for all the samples (see Table 4).

[000148] SEM cross-section images showed nickel deposition through all the depth of the 2x2 mm AI2O3-PTFE composites. Also, composites showed an increase in thickness and pore size distribution for samples with Ni loading 20 wt.% and 25 wt.%. SEM images of the 25 wt.% NiO/Al2O3 powder sample showed nickel oxide (NiO) particles and platelets of approximately 50-100 nm and 0.2-3 microns, respectively. Similar nickel oxide morphology was observed for the 25 wt.% NiO/Al2O3-PTFE composite sample. Apparent higher content of nickel was observed in the surface compared to inside of the composites. Only particles were observed on the inside of 25 wt.% NiO/Al2O3-PTFE composite samples. SEM images of the 10 wt.% NiO/Al2O3-PTFE composite samples showed Ni particles well dispersed on the surface of the alumina while no Ni is evident on the PTFE. SEM images for the 1 wt.% Ni/Al2O3-PTFE composite samples show fewer and smaller particles on the alumina particles.

[000149] BET analysis was performed. Surface area of alumina does not change when incorporated to the porous PTFE matrix. The alumina powder and the AI2O3-PTFE composites have similar BET surface area when normalized by alumina content. The surface area of the alumina powder and AI2O3-PTFE composite decrease with the nickel impregnation as expected (see Table 4).

[000150] Impregnations of 20 wt.% Ni into alumina particles and AI2O3-PTFE composites of two different porosities were done (see Table 5). These samples showed more uniform catalyst distribution compared to the 25 wt.%. Nickel content measured by ICP in agreement with theoretical values. Surface area for the 20NiO/Al2O3 powder and 20NiO/Al2O3-ePTFE composite were 20.0 m²/g and 13.5 m²/g, respectively. Similar values were determined when normalized by amount of alumina or nickel in the samples (see Table 5). SEM images of 20 wt.% NiO/Al2O3- PTFE composite sample showed well-dispersed nickel particles on the alumina particles and not the PTFE matrix (see Figure 4).

[000151 ] Temperature programmed reduction (TPR) was used to determine the reduction temperature of the nickel sample. Approximately 0.4 grams of sample were loaded into a U-shaped quartz tube flow cell holder (Quantachrome by Anton Paar). The inlet diameter of the cell is 12 mm. The exit side of the cell has a capillary bore. A small quantities of quartz wool were placed at the bottom of the tube to prevent elutriation of sample to the capillary. The sample was then added to the cell followed by another small amount of quartz wool and a filler quartz tube rod that reduced the void volume of the inlet section. The sample was heated to 275°C with a heating rate of 20°C/min under He flow (approximately 50 cc/min). Flow of He was continued for 120 min at that temperature. The sample was then cooled to 60 °C under He flow. Once temperature stabilized, the flow was switched to 3.8% H2/N2 for 35 min at 60°C. Then the temperature was increased to 275°C with a ramp rate of 1 .5 °C/min under 3.8% H2/N2 flow. The TCD and MS were recorded during the heat ramp. For the 20 wt.% NiO/Al2O3-PTFE composites, nickel oxide reduction has two peaks at 230 °C and 250 °C.

TABLE 1

Properties of the v-alumina particles and porous PTFE composite films including the immobilized v-alumina particles

TABLE 2

Number of ALD cycles, Pd thickness and grow per cycle (GPC) data of the silicon wafer test deposition

TABLE 3

Number of ALD cycles, Pd thickness, grow per cycle (GPC), Pd loading by ICP and Pd surface area by CO chemisorption of the y-alumina particle-filled PTFE composites after Pd ALD coating

TABLE 4

Amount of nickel and surface area for the AI2O3-PTFE samples after nickel impregnation with different loadings and calcination.

Note: ‘theoretical value in the alumina

TABLE 5

Amount of nickel and surface area for the samples after 20 wt.% of nickel impregnation and calcination.

Note: ‘theoretical value in the alumina

[000152] The invention of this application has been described above both generically and with regard to specific embodiments. It will be apparent to those skilled in the art that various modifications and variations can be made in the embodiments without departing from the scope of the disclosure. Thus, it is intended that the embodiments cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.

Claims

WHAT IS CLAIMED IS:

1. A method comprising: providing a porous composite comprising a plurality of support substrate particles non-covalently enmeshed within a porous fibrillated polymer matrix; and applying a catalyst coating to the porous composite such that the catalyst coating is selectively deposited substantially on the support substrate particles; whereby a catalyst coated composite is formed.

2. The method of claim 1 , wherein the porous fibrillated polymer matrix comprises a polymer having a surface energy of less than 35 dyne/cm.

3. The method of any of the preceding claims, wherein the support substrate particles have a surface energy that is at least 1 .5 times the polymer surface energy.

4. The method of any of the preceding claims, wherein the support substrate particles have a surface energy of at least 60 dyne/cm.

5. The method of any of the preceding claims, wherein more than 95 wt.% of the catalyst coating is deposited on the support substrate particle, based on a total amount of the catalyst coating applied to the porous composite.

6. The method of any of the preceding claims, wherein the catalyst coating has a loading range of from 0.01 % to 40 wt.% based on a total amount of the catalyst coating applied to the porous composite.

7. The method of any of the preceding claims, wherein the catalyst coated composite is porous.

8. The method of any of the preceding claims, wherein the catalyst coated composite is characterized by a catalyst coating gradient (through the Z-axis).

9. The method of any of the preceding claims, wherein the catalyst coating comprises a high-loading catalyst; wherein more than 10 wt.% of the catalyst coating is deposited on the support substrate particle, based on a total amount of the catalyst coating applied to the porous composite.

10. The method of any of the preceding claims, wherein the catalyst coating comprises a low-loading catalyst; wherein less than 2 wt.% of the catalyst coating is deposited on the support substrate particle, based on a total amount of the catalyst coating applied to the porous composite.

11 . The method of any of the preceding claims, wherein the ratio of the catalyst coating deposited on the support substrate to the catalyst coating deposited on a surface of the porous fibrillated polymer matrix is from 1000:1 to 1 .1 :1 .

12. The method of any of the preceding claims, wherein the support substrate particles are porous or nonporous.

13. The method of any of the preceding claims, wherein the support substrate particles have a surface area of from 10 to 5000 m²/g.

14. The method of any of the preceding claims, wherein the support substrate particles comprise a metal oxide, silica, clays, diatomaceous earth, zeolites, carbon, activated carbon, or any combination thereof.

15. The method of claim 14, wherein the metal oxide comprises AI2O3 or TiO2.

16. The method of claim 14, wherein the diatomaceous earth comprises kieselguhr.

17. The method of claim 14, wherein the zeolites comprise X, Y, A, or Zeolite Socony

Mobil (ZSM).

18. The method of any of the preceding claims, wherein the catalyst coating is applied to the support substrate particles by wet impregnation, coating, imbibing, chemical vapor deposition, atomic layer deposition (ALD), or any combination thereof.

19. The method of claim 18, wherein the catalyst coating is applied to the porous composite by ALD.

20. The method of any of the preceding claims, wherein the catalyst coating comprises a platinum family catalyst, a non-platinum family catalyst, metal oxides, ionic liquids, or any combination thereof.

21 . The method of any of the preceding claims, wherein the porous fibri Hated polymer matrix comprises an expanded polytetrafluoroethylene or an ultra-high molecular weight polyethylene.

22. The method of any of the preceding claims, wherein the catalyst coating is applied at a temperature from 10°C to 250°C.

23 The method of claim 22 wherein the applied catalyst coating is subsequently subjected to a heat treatment.

24. The method of any of the preceding claims, further comprising preparing a catalytic article comprising the porous composite and the catalyst coating.

25. The method of any of the preceding claims, wherein the catalyst coating is applied to the porous composite using a batch process, a continuous process, or a roll- to-roll process.

26. The method of any of the preceding claims, wherein the providing the porous composite comprises coating the porous fibrillated polymer matrix with the plurality of support substrate particles using ALD.

27. The method of any of the preceding claims, further comprising applying an additional coating to the catalyst coating; wherein the additional coating may be a promoter coating or a protective coating.

28. The method of claim 27, wherein the additional coating is applied to the catalyst coating by ALD.

29. A catalytic article comprising: a porous composite comprising a plurality of support substrate particles non- covalently enmeshed within a porous fibrillated polymer matrix; and a catalyst coating deposited on the support substrate particles, whereby a catalytic article is formed, wherein the catalytic article is characterized by a catalyst coating gradient through the Z-axis.

30. The catalytic article of claim 29, wherein the porous fibrillated polymer matrix comprises a polymer having a surface energy of less than 35 dyne/cm.

31 . The catalytic article of claims 29 or 30, wherein the support substrate particles have a surface energy that is at least 1.5 times the polymer surface energy.

32. The catalytic article of any of claims 29 to 31 , wherein the support substrate particles have a surface energy of at least 60 dyne/cm.

33. The catalytic article of any of claims 29 to 32, wherein more than 95 wt.% of the catalyst coating is deposited on the support substrate particle, based on a total amount of the catalyst coating applied to the porous composite.

34. The catalytic article of any of claims 29 to 33, wherein the catalytic article is porous.

35. The catalytic article of any of claims 29 to 34, wherein the catalyst coating forms a gradient around the plurality of support substrate particles.

36. The catalytic article of claim 35, wherein the gradient is formed from an outer surface of the catalyst coating to an interior surface of the porous composite.

37. The catalytic article of any of claims 29 to 36, wherein the catalyst coating has a thickness of from 0.01 nm to 1 pm as measured from the outer surface of the catalyst coating to the surface of the support substrate particles.

38. The catalytic article of any of claims 29 to 37, wherein the catalyst coating has a depth of from 0.1 nm up to 100% of the thickness of the porous composite as measured from the surface of the support substrate particles to the interior surface of the porous composite.

39. The catalytic article of any of claims 29 to 38, wherein the catalyst coating comprises a platinum family catalyst, a non-platinum family catalyst, metal oxides, ionic liquids, or a combination thereof.

40. The catalytic article of any of claims 29 to 39, wherein the catalytic article includes less than 25 wt.% of the catalyst coating based on a total amount of the catalyst coating applied to the porous composite.

41 . The catalytic article of any of claims 29 to 40, wherein the porous composite has a porosity of from 5% to 95 % prior to application of the catalyst coating.

42. The catalytic article of any of claims 29 to 41 wherein the catalytic article has a porosity of at least 50%.

43. The catalytic article of any of claims 29 to 42, wherein the porous composite has a surface area of from 50 to 5000 m²/g.

44. A method comprising: providing a porous composite comprising: a plurality of support substrate particles non-covalently enmeshed within a porous fibrillated polymer matrix; and a plurality of heterogeneous catalyst particles substantially deposited on the support substrate particles to form a catalyst coating; and applying an additional coating to the porous composite such that the additional coating is deposited on the catalyst coating.

45. The method of claim 44, wherein the additional coating is a promoter coating or a protective coating.

46. A process to catalytically convert a reactant to a product comprising: providing a fluid matrix comprising the reactant; contacting under suitable reaction conditions the fluid matrix with the catalytic article of any of claims 29 to 43; whereby the reactant is converted to a product by the catalytic article; and optionally recovering the product from the fluid matrix.

47. The process of claim 46 wherein the fluid matrix is a liquid, gas, or combination thereof.

48. The process of any of claims 46 to 47 wherein the fluid matrix is aqueous or nonaqueous.

49. The process of any of claims 46 to 48 wherein the process is a batch process or a continuous process.