WO2019193432A1

WO2019193432A1 - Metal coated hollow zeolites, methods of making, and uses thereof

Info

Publication number: WO2019193432A1
Application number: PCT/IB2019/051338
Authority: WO
Inventors: Ugo RAVON; Abdulrahman AL-HAZMI; Mohammed AL-HARBI; Khalid Albahily
Original assignee: Sabic Global Technologies B.V.
Priority date: 2018-04-02
Filing date: 2019-02-19
Publication date: 2019-10-10

Abstract

Supported catalysts are described. A supported catalyst can include a hollow zeolite support and a catalytic metal or metal oxide coating. The metal or metal oxide coating can be on at least a portion of the interior surface of the hollow zeolite support. Notably, the metal or metal oxide coating is not present on the exterior surface of the hollow zeolite support. Methods of making and using the supported catalytic metal coated hollow zeolite catalysts are also described.

Description

METAL COATED HOLLOW ZEOLITES, METHODS OF MAKING, AND USES

THEREOF

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority of U.S. Provisional Patent Application

No. 62/651,403 filed April 2, 2018, which is hereby incorporated by reference in its entirety.

BACKGROUND OF THE INVENTION

A. Field of the Invention

[0002] The invention generally concerns a supported catalyst that includes a hollow zeolite support and a catalytic metal or metal oxide coating on at least a portion of the interior surface of the support and not on the exterior surface of the support.

B. Description of Related Art

[0003] In view of the current environmental challenges, there is a need to develop a more sustainable chemical industry through more efficient chemical transformations and processes. Improvements in these chemical transformations and processes can include the (i) enhancement of the reaction yield and/or selectivity, (ii) reduction of operating cost, and (iii) use of more suitable reactants and catalysts. One approach to addressing the inefficiencies and cost of current processes is by developing new highly selective and cost-effective catalysts, as well as more efficient and cost effective methods of making the catalyst.

[0004] Zeolites are a family of crystalline materials that can be used in the design and development of new catalysts and catalyst supports. Zeolites have a porous structure that can accommodate a wide variety of cations, such as Na⁺, K⁺, Ca²⁺, Mg²⁺ and others. Currently, there are more than 200 different zeolite types registered and referenced by the International Zeolite Association (IZA). Due to their porosity and their high surface area, zeolites are used as catalyst and/or a catalyst supports. Metals can be deposited in the pores and on the surface of a zeolite, or incorporated into the zeolite framework in order to enhance specific reactions. By way of example Canadian Patent No. 1063087 to Retallick describes processes for preparing coated monolithic structures with an active metal oxide coating in the channels of the monolith and on the outside surface of the monolith. This process suffers in that the metallic particles can diffuse through the pores rendering the catalyst unstable. In most of the cases, this leaching effect is the main deactivation process. [0005] Encapsulation of metal nanoparticles in a zeolite structure can improve the physical and catalytic properties of the zeolite. Encapsulation can protect the individual nanoparticles from contact with other nanoparticles, thereby preventing sintering of the nanoparticles when subjected to elevated temperatures. Post-treatment deposition of nanoparticles inside zeolites has been reported, but the post-synthesis treatments result in nanoparticles in the cages and/or in the pores of the zeolite. By way of example International Application Publication No. WO 2016/038020 to Van Bokhoven etal. describes metal@hollow HZSM-5 materials and methods of making such materials. This process suffers in that it can be difficult to control the size, location, and retention of the nanoparticles in these post-treatment zeolite compositions.

[0006] Selective removal of external Ni nanoparticles on Ni@silicalite-l single crystal nanoboxes has been described Laprune etal. ( Applied Catalysis, 2017, 535, pages 69-76). This process uses citric acid to selectively leach out most of the external nickel particles from a Ni@silicalite-l material. This method suffers in that the treatment does not completely remove the external metal particles, and thus leaching of the active metal from the support can occur.

[0007] While various methods have been developed to encapsulate metals in zeolites, these catalysts can suffer in that a minimal number of active sites are produced, which in turn affects the reactivity/reaction rate of the reaction to be catalyzed.

SUMMARY OF THE INVENTION

[0008] A discovery has been made that provides a solution to at least some of the problems associated with catalytic metal encapsulated zeolite catalysts. The solution is premised on a supported catalyst that include a catalytic metal or metal oxide and a hollow zeolite. The metal encapsulated zeolite can include a metal or metal oxide coating on the interior surface of the hollow portion of the zeolite. Notably, the metal or metal oxide coating is not present on the exterior surface of the support. Without wishing to be bound by theory, it is believed that this catalyst morphology can reduce leaching of the catalytic metal from the zeolite while maintaining or increasing selectivity of the chemical reaction.

[0009] In one aspect of the invention, zeolite supported catalysts are described. A supported catalyst can include a hollow zeolite support having an exterior surface and an interior surface that defines and encloses a hollow space within the interior of the support. A catalytic metal or metal oxide coating can be present on at least a portion of the interior surface of the support. The coating can cover at least 50% (e.g., 50%, 60%, 70%, 80%, 90%, 100 %) of the interior surface and/or have a thickness of 0.5 nanometers (nm) to 5 nm. The catalytic metal or metal oxide coating is not present on the exterior surface of the support. Hollow zeolite supports can have an AEL, FER, LTL, TON, MFI, a FAET, an ITH, a *BEA, a MOR, a LTA, a MWW, a CHA, a MER, or a VFI type framework, preferably a MFI type framework. In some embodiments, the zeolite support is a hollow silicate- 1 zeolite. The catalytic metal or metal oxide coating can include a Column 1 metal, a Column 2 metal, a transition metal, post- transition metal, or lanthanide metal or any allow or combination thereof. In some embodiments, the metal or metal oxide coating includes iron (Fe), aluminum (Al), gallium (Ga), or alloys thereof, or combinations thereof. In one embodiment, the metal oxide coating is a Ga203, a Fe203, or an AI2O3 coating. The AI2O3 coating can be a gamma AI2O3 (y-AEOs) coating. In some aspects, the framework and/or internal portions ( e.g ., pores and channels) of the hollow zeolite support does not include catalytic metal or metal oxide and/or the hollow space does not include any catalytic metal or metal oxide particles (e.g., nanoparticles). The catalyst can include at 0.5 wt.% to 10 wt.% of the catalytic metal or metal oxide coating and/or 90 to 99.5 wt.% of the hollow zeolite support.

[0010] Methods of catalyzing a chemical reaction using the catalyst of the present invention are described. A method can include contacting a reactant feed with the supported catalyst of the present invention and producing a chemical compound from the reactant feed.

[0011] In yet another aspect, methods of making the supported catalyst are described. A method can include: (a) contacting a hollow zeolite support having an exterior surface and an interior surface that defines and encloses a hollow space within the interior of the support with a metal precursor material to form a loaded hollow zeolite support having at least a portion of the metal precursor material positioned within the hollow space of the support; (b) drying the loaded hollow zeolite support; (c) washing the dried loaded hollow zeolite support to remove metal precursor material present on the exterior surface of the support while retaining the metal precursor material present in the hollow space of the support; and (d) calcining the washed loaded hollow zeolite support to form the supported catalyst of the present invention. Step (b) drying can be performed at a temperature of 20 °C to 100 °C until dry (e.g, for 8 hours to 12 hours. Washing step (c) can be performed with an aqueous solution and is preferably performed at least two times prior to performing step (d). Calcining step (d) can be performed at a temperature of 450 °C to 650 °C for 3 to 12 hours, preferably 500 °C to 600 °C for 4 to 8 hours. Steps (a), (b), and (c) can be repeated at least two times or at least 3 times or 4 times or more prior to performing calcining step (d). The metal precursor material can be a solution of metal salt solubilized in a solvent. Further, and without wishing to be bound by theory, the metal or metal oxide coating layer present on at least a portion of the interior surface of the hollow zeolite support can be formed from melting or sintering of a plurality of metal or metal oxide nanoparticles present within the hollow through the aforementioned calcination step.

[0012] In the context of the present invention 20 embodiments are described. Embodiment

1 is a supported catalyst comprising: (a) a hollow zeolite support having an exterior surface and an interior surface that defines and encloses a hollow space within the interior of the support; and (b) a catalytic metal or metal oxide coating that is coated onto at least a portion of the interior surface of the hollow zeolite support, wherein the catalytic metal or metal oxide coating is not present on the exterior surface of the hollow zeolite support. Embodiment 2 is the supported catalyst of embodiment 1, wherein the hollow zeolite support has a AEL, FER, LTL, TON, MFI, a F AU, a ITH, a *BEA, a MOR, a LTA, a MWW, a CHA, a MER, or a VFI type framework. Embodiment 3 is the supported catalyst of embodiment 2, wherein the hollow zeolite support has a MFI type framework. Embodiment 4 is the supported catalyst of embodiment 3, wherein the hollow zeolite support is silicate-l . Embodiment 5 is the supported catalyst of any one of embodiments 1 to 4, wherein the catalytic metal or metal oxide coating is a Column 1 metal, a Column 2 metal, a transition metal, post-transition metal, or lanthanide metal or metal oxide coating or any alloy or combination thereof. Embodiment 6 is the supported catalyst of embodiment 5, wherein the catalytic metal or metal oxide coating is an iron (Fe), aluminum (Al), gallium (Ga), or tungsten (W) metal or metal oxide coating or any alloy or combination thereof. Embodiment 7 is the supported catalyst of embodiment 1, wherein the hollow zeolite support is silicate-l and the catalytic metal or metal oxide coating is a Ga203 coating. Embodiment 8 is the supported catalyst of embodiment 1, wherein the hollow zeolite support is silicate-l and the catalytic metal or metal oxide coating is a Fe203 coating. Embodiment 9 is the supported catalyst of embodiment 1, wherein the hollow zeolite support is silicate-l and the catalytic metal or metal oxide coating is an AI2O3 coating, preferably a g-Aΐ2q3 coating. Embodiment 10 is the supported catalyst of any one of embodiments 1 to 9, wherein the framework of the hollow zeolite support does not include catalytic metal or metal oxide. Embodiment 11 is the supported catalyst of any one of embodiments 1 to 10, wherein the hollow space does not include catalytic metal or metal oxide nanoparticles. Embodiment 12 is the supported catalyst of any one of embodiments 1 to 11, wherein the catalytic metal or metal oxide coating coats at least 50%, 60%, 70%, 80%, 90%, or 100% of the interior surface. Embodiment 13 is the supported catalyst of any one of embodiments 1 to 12, wherein the catalytic metal or metal oxide coating has a thickness of 0.5 nanometers (nm) to 5 nm. Embodiment 14 is the supported catalyst of any one of embodiments 1 to 13, wherein the catalytic metal or metal oxide coating is 0.5 wt. % to 10 wt. % of the supported catalyst. Embodiment 15 is the supported catalyst of any one of embodiments 1 to 14, wherein the hollow zeolite support is 90 to 99.5 wt.% of the supported catalyst. Embodiment 16 is a method of catalyzing a chemical reaction, the method comprising contacting a reactant feed with the supported catalyst of any one of embodiments 1 to 15 and producing a chemical from the reactant feed. Embodiment 17 is a method of making the supported catalyst of any one of embodiments 1 to 15, the method comprising: (a) contacting a hollow zeolite support having an exterior surface and an interior surface that defines and encloses a hollow space within the interior of the support with a metal precursor material to form a loaded hollow zeolite support having at least a portion of the metal precursor material positioned within the hollow space of the support; (b) drying the loaded hollow zeolite support; (c) washing the dried loaded hollow zeolite support to remove metal precursor material present on the exterior surface of the support while retaining the metal precursor material present in the hollow space of the support; and (d) calcining the washed loaded hollow zeolite support to form the supported catalyst of any one of embodiments 1 to 15. Embodiment 18 is the method of embodiment 17, wherein: drying step (b) is performed at a temperature of 20 °C to 100 °C for 8 hours to 12 hours; washing step (c) is performed with an aqueous solution and is optionally performed at least two times prior to performing step (d); and/or calcining step (d) is performed at a temperature of 400 °C to 650 °C for 3 to 12 hours, preferably 450 °C to 600 °C for 4 to 8 hours. Embodiment 19 is the method of any one of embodiments 17 to 18, wherein steps (a), (b), and (c) are repeated at least two times or at least 3 times prior to performing calcining step (d). Embodiment 20 is the method of any one of embodiments 17 to 19, wherein the metal precursor material is a solution of metal salt solubilized in a solvent.

[0013] Other embodiments of the invention are discussed throughout this application. Any embodiment discussed with respect to one aspect of the invention applies to other aspects of the invention as well and vice versa. Each embodiment described herein is understood to be embodiments of the invention that are applicable to other aspects of the invention. It is contemplated that any embodiment or aspect discussed herein can be combined with other embodiments or aspects discussed herein and/or implemented with respect to any method or composition of the invention, and vice versa. Furthermore, compositions of the invention can be used to achieve methods of the invention. [0014] The following includes definitions of various terms and phrases used throughout this specification.

[0015] The phrase“intra-particle hollow space” refers to a hollow space or void in within the interior surface of a zeolite shell. FIG. 1 A provides a non-limiting example of a particle of the present invention that includes a single intra-particle hollow space. FIG. 1B provides a non-limiting example of a particle of the present invention that includes two intra-particle hollow spaces.

[0016] The term“catalyst” refers to a single hollow zeolite particle or a plurality of hollow zeolite particles positioned adjacent to each other in a catalytic bed and/or shaped into a form that can catalyze a chemical reaction. FIGS. 1 A-1B provide non-limiting examples of catalysts of the present invention.

[0017] “Nanostructure” or“nanomaterial” refer to an object or material in which at least one dimension of the object or material is equal to or less than 1000 nm ( e.g ., one dimension is 1 to 1000 nm in size). In a particular aspect, the nanostructure includes at least two dimensions that are equal to or less than 1000 nm (e.g., a first dimension is 1 to 1000 nm in size and a second dimension is 1 to 1000 nm in size). In another aspect, the nanostructure includes three dimensions that are equal to or less than 100,000 nm (e.g., a first dimension is 1 to 1000 nm in size, a second dimension is 1 to 1000 nm in size, and a third dimension is 1 to 1000 nm in size). The shape of the nanostructure can be of a wire, a particle (e.g., having a substantially spherical shape), a rod, a tetrapod, a hyper-branched structure, a tube, a cube, or mixtures thereof. “Nanoparticles” include particles having an average diameter size of 1 to 1000 nanometers.

[0018] Particle size of the nanostructures or other particles can be measured using known techniques. Non-limiting examples include transmission electron spectroscopy (TEM), scanning electron microscopy (SEM), preferably TEM.

[0019] The terms“about” or“approximately” are defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment, the terms are defined to be within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.

[0020] The terms “wt.%,” “vol.%,” or“mol.%” refers to a weight percentage of a component, a volume percentage of a component, or molar percentage of a component, respectively, based on the total weight, the total volume of material, or total moles, that includes the component. In a non-limiting example, 10 grams of component in 100 grams of the material is 10 wt.% of component.

[0021] The term“substantially” and its variations are defined to include ranges within 10%, within 5%, within 1%, or within 0.5%.

[0022] The terms“inhibiting” or“reducing” or“preventing” or“avoiding” or any variation of these terms, when used in the claims and/or the specification includes any measurable decrease or complete inhibition to achieve a desired result.

[0023] The term“effective,” as that term is used in the specification and/or claims, means adequate to accomplish a desired, expected, or intended result.

[0024] The use of the words“a” or“an” when used in conjunction with any of the terms “comprising,”“including,”“containing,” or“having” in the claims, or the specification, may mean“one,” but it is also consistent with the meaning of“one or more,”“at least one,” and “one or more than one.”

[0025] The words“comprising” (and any form of comprising, such as“comprise” and “comprises”),“having” (and any form of having, such as“have” and“has”),“including” (and any form of including, such as“includes” and“include”) or“containing” (and any form of containing, such as“contains” and“contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

[0026] The hollow zeolite catalysts of the present invention can“comprise,”“consist essentially of,” or“consist of’ particular ingredients, components, compositions, etc. disclosed throughout the specification. With respect to the transitional phrase“consisting essentially of,” in one non-limiting aspect, a basic and novel characteristic of the hollow zeolite catalysts of the present invention are (1) a hollow zeolite support having an exterior surface and an interior surface that defines and encloses a hollow space within the interior of the support with a catalytic metal or metal oxide coating on at least a portion of the interior surface of the support, (2) no metal or metal oxide particle or coating is present on the exterior surface of the zeolite support, and optionally (3) their use in catalyzing chemical reactions.

[0027] Other objects, features and advantages of the present invention will become apparent from the following figures, detailed description, and examples. It should be understood, however, that the figures, detailed description, and examples, while indicating specific embodiments of the invention, are given by way of illustration only and are not meant to be limiting. Additionally, it is contemplated that changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. In further embodiments, features from specific embodiments may be combined with features from other embodiments. For example, features from one embodiment may be combined with features from any of the other embodiments. In further embodiments, additional features may be added to the specific embodiments described herein.

BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Advantages of the present invention may become apparent to those skilled in the art with the benefit of the following detailed description and upon reference to the accompanying drawings.

[0029] FIGS. 1A-B is a schematic of the supported catalyst of the present invention showing hollow zeolites with one (FIG. 1A) hollow space or two (FIG. 1B) hollow spaces having the metal or metal oxide coating on the interior surface of the hollow.

[0030] FIG. 2 is a schematic of a method of the present invention to prepare the supported catalyst of the present invention.

[0031] FIG. 3 is a schematic of a system to produce a chemical compound using the supported catalyst of the present invention.

[0032] FIG. 4 shows X-ray diffraction (XRD) patterns for Ga Hollow Silicalite-l (Ga- HS1), and hollow silicate-l (HS1) absent the coating; * peaks are gallium oxide.

[0033] FIGS. 5A and 5B show transmission electron microscopy (TEM, 5 A) and scanning transmission electron microscopy (STEM, 5B) images of Ga-HSl catalyst of the present invention at low magnification.

[0034] FIGS. 6A and 6B show TEM (6 A) and STEM (6B) images of Ga-HSl catalyst of the present invention at high magnification.

[0035] FIG. 7 shows XRD patterns for Fe-HSl and HS1; * peaks are iron oxide.

[0036] FIGS. 8A and 8B show TEM images of Fe-HSl catalyst at high magnification. Particles designated as A and B are fully coated Fe oxide (dark line) within hollow cavities. Particles designated as C are hollow cavities that are broken.

[0037] FIGS. 9A-9E shows STEM analysis (FIG. 9A)) and energy-dispersive X-ray spectroscopy (EDX) analysis carried out on different particle localizations (FIGS. 9B-9E) on Fe-HSl of the present invention. [0038] FIG. 9F is a schematic representation of the EDX pathway analysis of the Fe-HSl catalyst particles of the present invention.

[0039] FIG. 10 shows XRD patterns of HS1 (bottom) and A1-HS1 (top).

[0040] FIGS. 11A-11G shows EDX analysis (FIGS. 11B-11G) carried out on the particle locations shown in STEM (FIG. 11 A) of the A1-HS1 catalyst of the present invention.

[0041] While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings. The drawings may not be to scale.

DFTATEFD DESCRIPTION OF TTTF INVENTION

[0042] A solution to some problems associated with supported catalysts has been discovered. The solution is premised on the idea of coating an interior surface of a hollow zeolite with a catalytic metal or metal oxide layer. The coating layer can be a homogenous layer. Notably, the outer surface of the hollow zeolite does not include metal or metal oxide particles or a metal or metal oxide coating. The supported catalyst of the present invention can have high activity and selectivity as compared to other catalysts.

[0043] These and other non-limiting aspects of the present invention are discussed in further detail in the following sections with reference to the figures.

A. Catalyst Structure

[0044] The metal or metal oxide coated hollow zeolite structure of the present invention includes a metal or an oxide or alloy thereof coating (“metal coating” or“metal coated”) on the interior surface of a hollow space that is present in the zeolite. FIG. 1A is a cross-sectional illustration of a supported catalyst 100 having a metal coated/hollow zeolite structure. The catalyst material 100 has a zeolite shell 102, a metal coating 104 and hollow space 106. As discussed in detail below, the hollow space 106 can be formed by removal of a portion of the zeolite core during the making of the catalyst material. Shell 102 includes an inner surface 108 and outer surface 110. Inner surface 108 forms the interior surface to which the metal, metal oxide, or metal alloy coating 104 is attached. Inner surface 108 and outer surface 110 are made of the same zeolite material, or a combination of zeolite materials. As shown in FIG. 1 A, the metal coating 104 coats substantially all of the inner wall or interior surface 108 of hollow space 106. It should be understood that one or more portions of the interior surface may not include the metal coating ( i.e the inner surface can be partially coated). FIG. 1B depicts the metal coated hollow zeolite particle 100 having two hollow spaces. In certain aspects, 1% to 99%, 10% to 80%, 20% to 70%, 30% to 60%, 40% to 50% or any range or value there between of the inner surface 108 is coated. The pore size of the zeolite shell is the same or similar to the pore size of the starting zeolite ( e.g ., about 5.5 A). A volume space of the hollow space can be about 30 to 80%, 40 to 70%, or 50 to 60% of the zeolite particle volume or 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% or any value or range there between. The volume of the hollow space can be measured using transmission electron microscopy (TEM). The thickness of the metal or metal oxide coating on the interior surface of the hollow space can be 0.5 nm to 5 nm, or at least any one of, equal to any one of, or between any two of 0.5 nm, 1 nm, 1.25 nm, 1.5 nm, 1.75 nm, 2 nm, 2.25 nm, 2.5 nm, 2.75 nm, 3 nm, 3.25 nm, 3.5 nm, 3.75 nm, 4 nm, 4.25 nm, 4.5 nm, 4.75 nm, and 5 nm. The metal coating or layer 104 can have varying degrees of thickness such that the maximum thickness can be, for example, 5 nm, and the minimum thickness can be, for example, 0.5 nm. Alternatively, the metal coating or layer 104 can have a substantially consistent thickness. A thickness of the shell (e.g., zeolite) can range from 5 to 30 nm, preferably 10 nm to 20 nm, or 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, 11 nm, 12 nm, 13 nm, 14 nm, 15 nm, 16 nm, 17 nm, 18 nm, 20 nm, 21 nm, 22 nm, 23 nm, 24 nm, 25 nm, 26 nm, 27 nm, 28 nm, 29 nm, 30 nm, or any value or range there between. In some embodiments, the thickness is 0.5 to 2.5 nm. The thickness of the coating and hollow space can be measured using STEM.

1. Metal Coating

[0045] Metal coating 104 can include one or more catalytically active metals. The metal coating can include one or more Column 1 metals, Column 2 metals, transition metals or post transition metals of the Periodic Table. The metals can be obtained from metal precursor compounds. Non-limiting examples of Column 1 metals include lithium (Li), sodium (Na), potassium (K) rubidium (Rb) and cesium (Cs). Column 2 metals can include magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba). Non-limiting examples of transition metals include lanthanides (Ln), titanium (Ti), zirconium (Zr), vanadium (V), niobium (Nb), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), iron (Fe), rhenium (Re), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), nickel (Ni), iridium (Ir), palladium (Pd), platinum (Pt), copper (Cu), gold (Au), zinc (Zn), cadmium (Cd), mercury (Hg) or any combination thereof, or any oxide or alloy thereof. Non-limiting examples of post transition metals include aluminum (Al), gallium (Ga), indium (In), tin (Sn), lead (Pb), titanium (Ti), bismuth (Bi), or any combination thereof or any oxide or alloy thereof. In a particular instance, vanadium (IV) oxide, vanadium (V) oxide, iron (II) or (III) oxide, aluminum (III) oxide, gallium (III) oxide, niobium (III) oxide, or titanium (IV) oxide, or any combination thereof can be used. The metal coating can be obtained from a precursor material such as a metal nitrate, a metal amine, a metal chloride, a metal coordination complex, a metal sulfate, a metal phosphate hydrate, metal complex, or any combination thereof. Examples of metal precursor compounds include vanadium chloride, vanadium nitrate, iron nitrate nonahydrate, iron chloride, indium nitrate, indium chloride, aluminum nitrate, aluminum chloride, gallium nitrate hexahydrate, gallium trichloride, or niobium chloride, titanium isopropoxide, palladium acetate, palladium chloride, chloroplatinic acid, platinum acetyl acetonate, etc. These metals or metal compounds can be purchased from any chemical supplier such as MilliporeSigma® (St. Louis, Missouri, USA), Alfa-Aeaser (Ward Hill, Massachusetts, USA), and/or Strem Chemicals (Newburyport, Massachusetts, USA). The amount of precursor material can be determined based on the total weight percent of metal desired in the final catalyst. The weight ratio of the hollow zeolite support to the metal precursor material in step (a) can be 2: 1 to 100: 1, or at least any one of, equal to any one of, or between any two of 2: 1, 5: 1, 10:, 15: 1, 20: 1, 25: 1, 30: 1, 35: 1, 40: 1, 45: 1, 50: 1, 55: 1, 60: 1, 65: 1, 70: 1, 75: 1, 80: 1, 85: 1, 90: 1, 95: 1, 100: 1.

[0046] The amount of catalytic metal depends, inter alia , on the use of the catalysts (e.g., alkylation of hydrocarbons, hydrogenation of hydrocarbons, dehydrogenation of hydrocarbons, oxidation of hydrocarbons, oxygen dissociation of ethylene to ethylene oxide, acidic reactions, basic reactions, and the like). In some embodiments, the amount of catalytic metal present in the coating on the interior surface of the hollow ranges from 0.5 to 10 % by weight of catalyst, from 1 to 8 wt.% of catalyst or at least any one of, equal to any one of, or between any two of 0.5 wt.%, 1 wt.%, 1.5 wt.%, 2 wt.%, 2.5 wt.%, 3 wt.%, 3.5 wt.%, 4 wt.%, 4.5 wt.%, 5 wt.%, 5.5 wt.%, 6 wt.%, 6.5 wt.%, 7 wt.% 7.5 wt.%, 8 wt.%, 8.5 wt.%, 9 wt.%, 9.5 wt.% and 10 wt.% with the balance being zeolite support. If the catalyst includes more than one metal (e.g., M¹, M², and M³), M¹ and M², the catalyst includes 0.5 to 10 weight % of the total weight of the bimetallic coating or when M¹, M², and M³, the catalyst includes 0.5 to 10 weight % of the total weight of the trimetallic coating, based on the total weight of the catalyst.

2. Zeolite Material

[0047] The zeolite shell 102 (See, FIGS 1A and 1B) can be any porous zeolite or zeolite- like material. Zeolites have uniform, molecule-sized pores, and can be separated based on their size, shape and polarity. For example, zeolites have pore sizes ranging from about 0.3 nm to about 1 nm. The crystalline structure of zeolites can provide good mechanical properties and good thermal and chemical stability. The zeolite material can be a naturally occurring zeolite, a synthetic zeolite, a zeolite that have other materials in the zeolite framework ( e.g ., phosphorous), or combinations thereof. X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM) are used to determine the properties of zeolite materials, including their crystallinity, size and morphology. The network of zeolites is made up of Si0₄ and/or Al0₄ tetrahedra which are joined via shared oxygen bridges. An overview of the known structures may be found, for example, in W. M. Meier, D. H. Olson and Ch. Baerlocher,“Atlas of Zeolite Structure Types”, Elsevier , 5th edition, Amsterdam 2001. Non-limiting examples of zeolites include ABW, ACO, AEI, AEL, AEN, AET, AFG, AFI, AFN, AFO, AFR, AFS, AFT, AFX, AFY, AHT, ANA, APC, APD, AST, ATN, ATO, ATS, ATT, ATV, AWO, AWW, *BEA, BIK, BOG, BPH, BRE, CAN, CAS, CFI, CGF, CGS, CHA, CHI, -CLO, CON, CZP, DAC, DDR, DFO, DFT, DOH, DON, EAB, EDI, EMT, EPI, ERI, ESV, EUO, *EWT, FAU, FER, GIS, GME, GOO, HEU, IFR, ISV, ITE, ITH, ITG, JBW, KFI, LAU, LEV, LIO, LOS, LOV, LTA, LTL, LTN, MAZ, MEI, MEL, MEP, MER, MFS, MON, MOR, MSO, MTF, MFI, MTN, MTT, MTW, MWW, NAT, NES, NON, OFF, OSI, PAR, PAU, PHI, RHO, RON, RSN, RTE, RTH, RUT, SAO, SAT, SBE, SBS, SBT, SFF, SGT, SOD, STF, STI, STT, TER, THO, TON, TSC, VET, VFI, VNI, VSV, WIE, WEN, YUG and ZON structures and mixed structures of two or more of the abovementioned structures. In some embodiments, the zeolite includes phosphorous to form an AIPOx structure with the appropriate porosity. Non-limiting examples of AIPOx zeolites include AABW, AACO, AAEI, AAEL, AAEN, AAET, A AFG, AAFI, AAFN, A AFO, AAFR, AAFS, A AFT, AAFX, A AFY, AAHT, AANA, A APC, AAPD, AAST, AATN, AATO, AATS, AATT, AATV, AAWO, AAWW, ABEA, ABIK, ABOG, ABPH, ABRE, ACAN, ACAS, ACFI, ACGF, ACGS, ACHA, ACHI, A-CLO, ACON, ACZP, AD AC, ADDR, ADFO, ADFT, ADOH, ADON, AEAB, AEDI, AEMT, AEPI, AERI, AESV, AEUO, A*EWT, AFAU, AFER, AGIS, AGME, AGOO, AHEU, AIFR, AISV, AITE, AITH, AITG, AJBW, AKFI, ALAU, ALEV, ALIO, ALOS, ALOV, ALTA, ALTL, ALTN, AMAZ, AMEI, AMEL, AMEP, AMER, AMFI, AMFS, AMON, AMOR, AMSO, AMTF, AMTN, AMTT, AMTW, AMWW, ANAT, ANES, ANON, AOFF, AOSI, APAR, APAU, APHI, ARHO, ARON, ARSN, ARTE, ARTH, ARUT, AS AO, AS AT, ASBE, ASBS, ASBT, ASFF, ASGT, ASOD, ASTF, ASTI, ASTT, ATER, ATHO, ATON, ATSC, AVET, AVFI, AVNI, AVSV, A WIE, AWEN, AYUG and AZON structures and mixed structures of two or more of the abovementioned structures. In particular embodiments, the zeolite is a porous zeolite in pure silica (Si/Al= ¥) form or with a small amount of Al, for example, *BEA, MFI, silicalite-l, type Y or combinations thereof zeolites. The zeolite can have a Si/Al of 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 100, up to ¥, or any value or range there between. The zeolite of the present invention is a pure porous zeolite having none or substantially no acidic sites on the surface of the zeolite. The zeolite can be organophilic. Zeolites may be obtained from a commercial manufacturer such as Zeolyst (Valley Forge, Pennsylvania, U.S.A.).

B. Preparation Metal Coated/Hollow Zeolite Material

[0048] The catalysts of the present invention can be prepared by methodology known in the catalyst art. FIG. 2 is a schematic of methods to make a metal coated/hollow shell zeolite material of the present invention. In method 200, step 1, zeolite material 202 can be obtained either through a commercial source or prepared using the methods described in the Examples section. An aqueous solution of the metal precursor material ( e.g ., an iron, an aluminum, a gallium, a platinum, a palladium, a nickel, a cobalt, a manganese, a vanadium, a chromium, a silver, an indium, an alkali metal, an alkaline earth metal, a tin, or a cadmium precursor), or a combination of metal precursors (e.g., to make a coating having multiple metals coated on the interior and exterior surface of the hollow zeolite) can be contacted with the zeolite material to allow metal precursor material 204 to be positioned within hollow space 106 of the zeolite material 202 and form metal treated zeolite material 206. Zeolite material 206 can have metal precursor material 204 on exterior surface 110 of the zeolite and in hollow space 106 or within the pores or channels of the shell 102. The amount of solution (e.g, aqueous, alcoholic, or a mixture thereof) of metal precursor material is the same or substantially the same as the pore volume of the zeolite material. In some embodiments, the zeolite can be subjected to a vacuum prior to treating with the metal precursor solution (e.g., 100 to 300 °C, or 225 to 275 °C for 1 to 10 h or about 6 h under 10 ⁵ to 10 ⁷, or 10 ⁶ bar (10 ⁶ to 10 ⁸, or 1 O ⁷ MPa)) to facilitate diffusion of the metal precursor solution through the pores and/or to remove any Bronsted acid sites. In step 2, the metal treated zeolite material can be dried to obtain dried metal (e.g., mono-, bi- or tri-metallic) treated zeolite material 208. Drying conditions can include heating the metal treated zeolite material 206 from 30 °C to 100 °C, preferably 40 °C to 60 °C, for 4 to 24 hours. In some embodiments, metal treated hollow zeolite 206 is not dried. In step 3, metal treated zeolite material 206 can be washed with solvent (e.g, water) to produce washed metal treated zeolite material 208. The washing removes most, substantially all, or all metal precursor solution from exterior surface 110 of zeolite 202. Washing can be repeated at least 2, 3, 4, 5, up to 10 times. Steps 1, 2, and 3 can be repeated in sequence multiple times (e.g, 1, 2, 3, 4, 5, 6, etc.) until a desired amount of metal is loaded into the hollow space of the zeolite. It should be understood that when steps 1, 2, and 3 are repeated step 2 can be omitted or performed fewer times than treating step 1 and washing step 3. Washing step can include one or multiple washing each time treating step 1 is performed. The amount of wash can range from 2 to 10 times or more than the amount of starting hollow zeolite, or 2, 3, 4, 5, 6, 7, 8, 9, 10 or more times or any value or range there between.. In step 4, the resulting washed metal treated zeolite material 208 can be heated in the presence of an oxygen source ( e.g ., calcined in air) to transform the metal precursor solution to a metal or metal oxide coating that coats interior surface 108 of hollow zeolite material 100. As illustrated in FIG. 2, the coating can be homogenous rather than a plurality of particles present on the interior surface of 108 of the support. Without wishing to be bound by theory, it is believed that the calcining step can sinter together and/or melt the precursor material 204 to form the coating. The zeolite material has metal or metal oxide coating or layer 104 attached to the interior surface 108 of the hollow space 106 in the zeolite shell 102. Calcination conditions can include a temperature of 450 °C to 650 °C, preferably 500 °C to 600 °C and a time of 3 to 12 hours, preferably 4 to 8 hours. Longer or shorter times can be used.

C. System and Method for Production of Chemical Compounds

[0049] Also disclosed are systems and methods of producing chemical compounds using the catalyst of the present invention. Reaction conditions can include contacting the catalyst materials 100 discussed above and/or throughout this specification having an active metal site (e.g., iron (II) or (III) oxide) with the one or more reactants (e.g., ethylene, propylene, benzene etc) under sufficient conditions to produce a product (e.g., ethylbenzene, cumene, etc). Non limiting examples of chemical reactions include a hydrocarbon hydroforming reaction, a hydrocarbon hydrocracking reaction, a hydrogenation of hydrocarbon reaction, a dehydrogenation of hydrocarbon reaction, oxidation reactions, oxygen dissociation reactions, acidic reactions, basic reactions and the like. For example, a catalyst of the present invention that includes Pt, Pd or PtPd metal or metal oxide coated on the interior surface of a hollow zeolite can be used for hydrogenation and/or dehydrogenation reactions. Oxygen dissociation reactions of ethylene to ethylene oxide can use a catalyst of the present invention that include Ag metal or metal oxide coated on the interior surface of a hollow zeolite. Oxidation of hydrocarbon reactions can use a catalyst of the present invention having Ni, Co, Mn, V, Cr, Pd, Pd (e.g, Columns 9-11 metals) or any combination thereof coated on the inside surface of the hollow zeolite. Acidic reactions can use a catalyst of the present invention having Al, Ga, In, Fe(III) or any combination thereof coated on the inside surface of the hollow zeolite. Basic reactions can use a catalyst of the present invention having Column 1, Column 2, Sn, Cd or any combination thereof coated on the inside surface of the hollow zeolite.

[0050] Reaction conditions can include temperature, pressure, space velocity or any combination thereof and can be varied depending on the type of reaction and/or equipment employed. The temperature, pressure, and GHSV can be varied depending on the reaction to be performed and is within the skill of a person performing the reaction ( e.g ., an engineer or chemist). Reaction temperatures can include a temperature range of 150 °C to 400 °C from 200 °C to 350 °C or from 2500 °C to 300 °C or 150 °C, 175 °C, 200 °C, 225 °C, 250 °C, 275 °C, 300 °C, 325 °C, 350 °C, 375 °C, 400 °C, or any value there between, a pressure range of about 5 bara (0.5 MPa) to 70 bara (7 MPa), a gas hourly space velocity (GHSV) ranging from 1,000 to 100,000 h ¹, or any combination thereof.

[0051] In some embodiments, the metal oxide coated hollow zeolite catalysts of the present invention are subjected to hydrogenation temperatures and pressures to reduce the catalytic metal oxide to catalytic metal particles. The conditions can include a temperature in the range of from about 75° C to about 750° C, for about 0.5 to about 48 hours at a pressure of about 0.01 MPa to about 8 MPa. The hydrogen source for the reduction of the metal oxide can be a gaseous mixture that includes 0.5 wt.% to 100 wt.% hydrogen and 0 wt.% to 99.5 wt.% unreactive gas (inert gas). The gas composition can be varied depending on the temperature, pressure, and/or desired metal particle size. Upon conversion from the metal oxide to metal, the reduced catalytic metal particle(s) can disconnect from the inner surface of the hollow portion of the zeolite (break the oxide coating) and be positioned within the hollow portion of the zeolite. Without wishing to be bound by theory, it is believed that in situ formation of a catalytic metal particle can enhance the life of the catalyst by reducing coking or carbon formation on the active metal site or prevent the sintering by segregating the metal particle from each other (e.g., one particle in a first hollow zeolite and another hollow particle in a second hollow zeolite particle). In certain aspects, carbon formation or coking is reduced or does not occur on the catalyst material 100, leaching is reduced or does not occur with the catalyst material 100, and/or sintering is reduced or does not on occur with the catalyst material 100. Furthermore, selectivity towards the product can be obtained in greater than 90 wt.%, 95 wt.% or 99.9 wt.% based on the weight of the total product stream.

[0052] Systems for producing chemical compounds are also described. FIG. 3 depicts a schematic for a system to produce a chemical compound. The system 300 can include an inlet 302 for a first reactant feed, an inlet 304 for a second reactant feed, a reaction zone 306 (e.g., a continuous flow reactor selected from a fixed-bed reactor, a fluidized reactor, or a moving bed reactor) that is configured to be in fluid communication with the inlets 302 and 304, and an outlet 308 configured to be in fluid communication with the reaction zone 306 and configured to remove a product stream from the reaction zone. The reactant zone 306 can include a catalyst of the present invention. The first reactant feed can enter the reaction zone 306 via the inlet 302. After a sufficient amount of the first reactant and catalyst have been placed in the reaction zone 306, an optional second reactant feed can enter the reaction zone through the feed inlet 304. In some embodiments, the first and/or second reactant feeds can be used to maintain a pressure in the reaction zone 306. In some embodiments, the reactant feed streams include inert gas ( e.g ., nitrogen or argon). In some embodiments, the reactant feeds are provided at the same timer or in reverse order. In some embodiments, only one reactant feed is used. In other embodiments, 3 or more reactant feeds are used. After a sufficient amount of time, the product stream can be removed from the reaction zone 306 via product outlet 308. The product stream can be sent to other processing units, stored, and/or transported.

[0053] System 300 can include one or more heating and/or cooling devices (e.g., insulation, electrical heaters, jacketed heat exchangers in the wall) or controllers (e.g., computers, flow valves, automated values, etc) that can be used to control the reaction temperature and pressure of the reaction mixture. While only one reactor is shown, it should be understood that multiple reactors can be housed in one unit or a plurality of reactors housed in one heat transfer unit.

EXAMPLES

[0054] The present invention will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes only, and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of noncritical parameters which can be changed or modified to yield essentially the same results.

[0055] Materials: Silicalite-l, tetrapropyl ammonium hydroxide (TPA(OH)), gallium nitrate hexahydrate (Ga(N03)3.6H₂0), iron (III) nitrate nonahydrate (FeN309.9H₂0), and aluminum nitrate nonahydrate (Al(N03)3.9H₂0) were purchased from MilliporeSigma (U.S.A.)

[0056] Characterization: The catalyst synthesized were systematically characterized by using XRD diffraction and TEM analysis. Powder X-ray diffraction (XRD) patterns were recorded on a PANalytical Empyrean X-ray (Malvern Panalytical B.V, the Netherlands) using a nickel-filtered CuKa X-ray source, a convergence mirror and a PIXcelld detector. The scanning rate was 0.01° over the range between 5° and 80° 20. Imaging was performed using a Titan G2 80-300 kV transmission electron microscope (FEI Company, a ThermoFischer Scientific Co., U.S.A) operating at 300 kV equipped with a 4 k ^c 4 k CCD camera, a GIF Tridiem (Gatan, Inc. U.S.A.) and an energy-dispersive X-ray spectroscopy detector (ED AX).

Example 1

(Hollow silicalite-1 (HS1) synthesis)

[0057] General Procedure: Silicalite-l (1 g) was mixed with TPA(OH) (5 mL 0.2 mol/L). The mixture was then transferred into polytetrafluorethylene-lined autoclave (50 mL), and heated at 170 °C for 72 h. The resulting zeolite was recovered by centrifugation, washed 3 times with water, dried over the night at 100 °C and then calcined under air at 550 °C for 6 h.

Example 2

(Gallium coated into hollow silicalite-1)

[0058] HS1 (3 g, Example 1) was mixed with a solution of Ga(N03)3.6H₂0 (400 mg) in methanol (5 mL, liquid chromatography/mass spectral grade). The mixture was dried at room temperature and washed a minimum of three times with water ( e.g 3 x 15 mL). This treatment (mixing, drying and washing) was repeated three times. After three treatments, the metal treated zeolite was calcined under air at 550 °C for 6 h to form a gallium oxide coated into hollow zeolite.

Example 3

(Characterization of gallium oxide coated into hollow zeolite)

[0059] FIG. 4 shows an XRD pattern of the hollow silicalite-l and Ga oxide hollow zeolite. From this characterization, it was clear that MFI structure was retained after the treatment. Moreover, no other crystal phase was detected.

[0060] FIGS. 5 A and 5B show TEM and STEM images Ga oxide hollow zeolite, respectively taken at low magnification. FIGS. 6 A and 6B show TEM and STEM images of the Ga oxide hollow zeolite, respectively taken at high magnification. From these images, it was determined that hollow zeolites were produced and that almost all of the zeolite particles are hollow. Moreover, no Ga oxide has been detected outside the hollow cavity. The gallium oxide coating was detected on the interior surface of the hollow cavity (bright circle around dark hollow cavity in FIG. 6B). The thickness of the gallium oxide coating was determined to be about 1 to 2 nm and was extremely homogeneous. About 30% of the void in hollow particles were coated. The coated was confirmed by STEM and EDX analysis.

Example 4

(Iron oxide coated into hollow silicalite-1)

[0061] HS1 (3 g, Example 1) was mixed with a solution of FeN309.9H₂0 (700 mg) in of methanol (5 mL, liquid chromatography/mass spectral grade). The mixture was dried at room temperature and washed a minimum of three times with water ( e.g 3 xl5mL). This treatment (mixing, drying and washing) was repeated three times. After three treatments, the metal treated zeolite was calcined under air at 550 °C for 6 h to form an iron oxide coated into hollow zeolite.

Example 5

(Characterization of iron oxide coated into hollow zeolite)

[0062] FIG. 7 shows an XRD pattern of the hollow silicalite-l and iron oxide hollow zeolite. From this characterization, it was clear that MFI structure was retained after the treatment. Moreover, no other crystal phase was detected. The catalyst included about 4.4 wt.% iron oxide and 95.6 wt.% silicalite-l . Based on the theoretical calculation of 7.7 wt.% iron, it was determined that 43 wt.% of the iron was removed during the washing step.

[0063] FIGS. 8 A and 8B show TEM and STEM images iron oxide hollow zeolite, respectively taken at high magnification. From this analysis, it was determined that iron oxide coating was present, dark line, within the hollow. However, some of the zeolite’s particle did not contain iron oxide. Without being bound by theory, it is believed that incomplete hollow formation of some of the zeolite particles happened. If the hollow was not fully closed, water washing would remove all metal salt. This assumption was strongly supported by the TEM pictures as full hollow particles are detected on A and B and iron oxide coating was detected. On other hand, particles designated as C in FIG. 8B are particles where the hollow formation was complete and iron oxide coating was not detected.

[0064] FIG. 9A shows images obtained with STEM analysis. FIGS. 9B-9E show the EDX spectra. In the STEM image, the iron oxide coating is the bright part. FIG. 9F is a schematic of a cross-sectional view of the EDX analysis. The EDX analysis carried out on the position 1 (Pl) zeolite particle did not show any iron. That was consistent with the assumption that washing removes the iron oxide. From EDX analysis of position 2 (P2) at the center of the hollow zeolite particle, it was determined that iron was present. These results supported the assumption of a full coverage of iron oxide coating on the internal surface of the hollow. EDX analysis of position 3 (P3) of the edge of the hollow, the brightest part, had a very strong iron signal. The difference between the two iron peak intensity, P2 and P3, was due to the pathway of the EDX beam. From FIGS. 9A-E, it was determined that the amount of iron was higher on the edge of the hollow (P3) than the middle of the hollow (P2).

Example 6

(Aluminum oxide coated into hollow silicalite-1)

[0065] HS1 (3 g, Example 1) was mixed with a solution of Al(N03)3.9H20 (300 mg) in of methanol (5 mL, liquid chromatography/mass spectral grade). The mixture was dried at room temperature and washed a minimum of three times with water ( e.g 3 x 15 mL). This treatment (mixing, drying and washing) was repeated three times. After three treatments, the metal treated zeolite was calcined under air at 550 °C for 6 h to form an aluminum oxide coated into hollow zeolite.

Example 7

(Characterization of aluminum oxide coated into hollow zeolite)

[0066] FIG. 10 shows the XRD pattern of Hollow Silicalite-l (HS1) and Hollow Silicalite- 1 with g-alumina coating (A1-HS1). As in the gallium and iron examples, the silicalite-l structure was preserved after the hollow formation and after the impregnation. All the peaks can be attributed to MFI structure or g-alumina. However, it was determined through TEM characterization that only 90-95% of the particle are hollow, and about 20-30 % of the hollow particles are broken.

[0067] FIGS. 11A-11G shows the STEM and EDX analysis performed on the A1-HS1 sample. FIG. 11A is the STEM image. FIGS. 11B-11G show the EDX spectra. From this characterization, it was concluded that the method of the present invention produces encapsulate g-alumina within the hollow zeolite, (EDX taken at positions p20 (FIG. 11B) and p2l (FIG. 11C)). EDX analysis performed on the center of the hollow zeolite (p24 (FIG. 11D)) showed an Al signal, which was consistent with a full coating of the hollow zeolite. EDX analysis carried out on the zeolite particle itself, at positions p22, p23, and p25 (FIGS. 11E- 11G, respectively) did not show any Al. From this data, it was determined that the Al was incorporated into the framework. About 15 % of the particles were coated.

[0068] As shown and described, the present invention provides a supported hollow zeolite having a catalytic metal or metal oxide coating on the interior surface of the support without any metal oxide or metal on the exterior surface of the support. The methodology to prepare the zeolite catalyst of the present invention provides an elegant and efficient process to produce catalytically loaded hollow zeolites.

[0069] Although embodiments of the present application and their advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the embodiments as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the above disclosure, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein can be utilized. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.

Claims

1. A supported catalyst comprising:

(a) a hollow zeolite support having an exterior surface and an interior surface that defines and encloses a hollow space within the interior of the support; and

(b) a catalytic metal or metal oxide coating coated onto at least a portion of the interior surface of the hollow zeolite support,

wherein the catalytic metal or metal oxide coating is not present on the exterior surface of the hollow zeolite support.

2. The supported catalyst of claim 1, wherein the hollow zeolite support has a AEL, FER, LTL, TON, MFI, a FAU, an ITH, a *BEA, a MOR, a LTA, a MWW, a CHA, a MER, or a VFI type framework.

3. The supported catalyst of claim 2, wherein the hollow zeolite support has a MFI type framework.

4. The supported catalyst of claim 3, wherein the hollow zeolite support is silicate-l.

5. The supported catalyst of claim 1, wherein the catalytic metal or metal oxide coating is a Column 1 metal, a Column 2 metal, a transition metal, post-transition metal, or lanthanide metal or metal oxide coating or any alloy or combination thereof.

6. The supported catalyst of claim 5, wherein the catalytic metal or metal oxide coating is an iron (Fe), an aluminum (Al), a gallium (Ga), a tungsten (W), a platinum (Pt), a palladium (Pd), a nickel (Ni), a cobalt (Co), a manganese (Mn), a vanadium (V), a chromium (Cr), a silver (Ag), an indium (In), an alkali, an alkaline earth, a tin (Sn), a cadmium (Cd) metal or metal oxide coating or any alloy or combination thereof.

7. The supported catalyst of claim 1, wherein the hollow zeolite support is silicate-l and the catalytic metal or metal oxide coating is a Ga203 coating or a Fe203 coating.

8. The supported catalyst of claim 1, wherein the hollow zeolite support is silicate-l and the catalytic metal or metal oxide coating is a silver or silver oxide coating.

9. The supported catalyst of claim 1, wherein the hollow zeolite support is silicate- 1 and the catalytic metal or metal oxide coating is an AI2O3 coating, preferably a y-AkCb coating.

10. The supported catalyst of claim 1, wherein the framework of the hollow zeolite support does not include catalytic metal or metal oxide.

11. The supported catalyst of claim 1, wherein the hollow space does not include catalytic metal or metal oxide nanoparticles.

12. The supported catalyst of clam 1, wherein the catalytic metal or metal oxide coating coats at least 50%, 60%, 70%, 80%, 90%, or 100% of the interior surface.

13. The supported catalyst of claim 1, wherein the catalytic metal or metal oxide coating has a thickness of 0.5 nanometers (nm) to 5 nm.

14. The supported catalyst of claim 1, wherein the catalytic metal or metal oxide coating is 0.5 wt. % to 10 wt. % of the supported catalyst.

15. The supported catalyst of claim 1, wherein the hollow zeolite support is 90 to 99.5 wt.% of the supported catalyst.

16. A method of catalyzing a chemical reaction, the method comprising contacting a reactant feed with the supported catalyst of claim 1 and producing a chemical from the reactant feed.

17. A method of making the supported catalyst of claim 1, the method comprising:

(a) contacting a hollow zeolite support having an exterior surface and an interior surface that defines and encloses a hollow space within the interior of the support with a metal precursor material to form a loaded hollow zeolite support having at least a portion of the metal precursor material positioned within the hollow space of the support;

(b) drying the loaded hollow zeolite support;

(c) washing the dried loaded hollow zeolite support to remove metal precursor material present on the exterior surface of the support while retaining the metal precursor material present in the hollow space of the support; and (d) calcining the washed loaded hollow zeolite support to form the supported catalyst of claim 1.

18. The method of claim 17, wherein:

drying step (b) is performed at a temperature of 20 °C to 100 °C for 8 hours to 12 hours; washing step (c) is performed with an aqueous solution and is optionally performed at least two times prior to performing step (d); and/or

calcining step (d) is performed at a temperature of 400 °C to 650 °C for 3 to 12 hours, preferably 450 °C to 600 °C for 4 to 8 hours.

19. The method of claim 17, wherein steps (a), (b), and (c) are repeated at least two times or at least 3 times prior to performing calcining step (d).

20. The method of claim 17, wherein the metal precursor material is a solution of metal salt solubilized in a solvent.