Method for synthesizing hierarchical ordered crystalline microporous materials with long-range mesoporous order

Abstract

A method for synthesizing hierarchical ordered zeolites and zeolite-type materials is provided. The synthesized hierarchical ordered zeolites and zeolite-type materials formed by the methods herein possess a high degree of defined long-range mesoporous order. The method includes base-mediated reassembly by decomposition of the parent material to the level of the oligomeric structural building units of the parent material and minimization or avoidance of amorphization / structural collapse. The decomposition and self-assembly are comprehensively controlled to produce hierarchical ordered zeolites and zeolite-type materials by the methods herein.

Description

Technical Field

[0001] The present disclosure relates to a method for synthesizing hierarchical ordered crystalline microporous materials.

Background Art

[0002] Zeolite Zeolites are microporous aluminosilicate materials that possess a defined structure and uniform pore diameters that can be measured in nanometers or angstroms (Å) (the pores are typically up to about 20 Å maximum). Typically, zeolites contain framework atoms such as silicon, aluminum, and oxygen arranged as silica and alumina tetrahedra. Zeolites are generally hydrated aluminosilicates that can be made or selected by their controlled porosity and other properties, and typically contain cations, water, and / or other molecules located within the porous network. Hundreds of natural and synthetic zeolite frameworks exist for a wide range of applications. Many zeolites occur naturally and are mined extensively, while a large body of interdependent research has led to synthetic zeolites of a wide variety of structures and compositions. The unique properties of zeolites and the ability to tailor them for specific applications have led to their extensive use in industry as catalysts (e.g., for the catalytic cracking of hydrocarbons or as components in catalytic converters), molecular sieves, adsorbents (e.g., desiccants), ion exchange materials (e.g., water softeners), and for gas separation. Certain types of zeolites have found use in various processes in petroleum refining units and in many other applications. The pores of zeolites can form sites for catalytic reactions and can also form selective channels for the passage of certain compounds and / or isomers towards other exclusions. Zeolites can also possess acidity levels that, alone or with the addition of active components, enhance their effectiveness as catalytic materials or adsorbents. Below, only one of the hundreds of types of zeolites elucidated by the International Zeolite Association (IZA) will be described. Many of these properties and uses are well known.

[0003] Zeolite Y (also known as Na-Y zeolite or faujasite Y zeolite) is a well-known material whose zeolite has ion exchange, catalytic, and adsorption properties. Zeolite Y is also a useful starting material for generating other zeolites such as ultrastable Y zeolite (USY). Like typical zeolites, faujasite is synthesized from alumina and silica sources, dissolved in a basic aqueous solution, and crystallized. Faujasite zeolite has a framework designated as FAU by the IZA and is formed by a 12-ring structure made up of supercages with a pore opening diameter of about 7.4 angstroms (Å) and sodalite cages with a pore opening diameter of about 2.3 Å. Faujasite zeolite is characterized by a three-dimensional pore structure with pores running perpendicular to each other in the x, y, and z planes. The secondary building units can be positioned at 4, 6, 6-2, 4-2, 1-4-4, or 6-6. The exemplary range of the silica-to-alumina ratio (SAR) for faujasite zeolite is from about 2 to about 6 and typically has unit cells (unit a, b, and c) in the range of about 24.5 to 24.85 Å. Faujasite zeolite is typically regarded as X-type when the SAR is about 2-3 and Y-type when the SAR is greater than about 3, for example, when it is about 3-6. Typically, faujasite is in the sodium form and can be ion-exchanged with ammonium, and the ammonium form can be calcined to convert the zeolite to its proton form.

[0004] Mesoporous silica While the zeolite has found great utility in its ability to select between small molecules and various cations, mesoporous solids (pores between about 20 and 500 Å) offer potential for applications involving chemical species that are up to an order of magnitude larger in size, such as nanoparticles and enzymes. The relatively bulky nature of such chemical species hinders diffusion through the microporous zeolite network, and thus, a larger porous system is required to effectively perform a similar molecular sieving action for larger chemical species.

[0005] Mesoporous silica is amorphous; however, it has pores with a periodically arranged pore structure and long-range order with a uniform pore diameter at the mesoscale. Mesoporous silica provides a high surface area and can be used as a host material to introduce additional functionality for a variety of applications such as adsorption, separation, catalysis, drug delivery, and energy conversion and storage.

[0006] Ordered structure The attractive properties of ordered structures are that their architecture can be described in terms of their symmetry. Crystals of a defined shape are associated with a defined arrangement of sub-units that make up the crystal, and thus the symmetry of the crystal is related to the symmetry of the sub-units. For example, seven clearly different three-dimensional crystal units are presented in Table 1. Crystal systems can be subdivided on the basis of the symmetry elements present, which are collectively called point groups and are presented in Table 2. For example, 3m implies the presence of a mirror plane with a three-fold axis of rotation. In the 3 / m (or 6) class, the mirror plane is perpendicular to the three-fold axis of rotation. In two-dimensional spaces such as lamellar systems with fewer dimensions than 3D, there are four crystal systems: hexagonal, square, rectangular, and orthorhombic.

[0007] Hierarchical ordered zeolite The defined microporous structure of zeolites provides a blend of important physicochemical functionalities that are highly desirable in various industrial practices. Their molecular-sized pore channels, embedded with adjustable acid / base sites, can geometrically distinguish the entry of guest species and govern shape-selective transformations. Such remarkable properties uniquely exhibited by zeolites demonstrate unprecedented importance in numerous chemical technologies, including but not limited to petroleum refining, detergents, and wastewater reduction, which deeply impact the world economy and environment. However, the performance of zeolites is often hampered as a result of their insufficient mass transfer induced by configurational diffusion within narrow micropores. Therefore, alleviating the essential mass transfer limitations is crucial for exploring the maximum potential of zeolites in diverse energy economies and thereby enhancing the accessibility to internal functional sites. Another drawback of microporous zeolites as catalysts in certain reactions is their susceptibility to coking, which can lead to accelerated catalyst deactivation and product selectivity.

[0008] In this regard, hierarchically ordered zeolites (HOZs) possessing an ordered mesoporous structure and zeolite mesoporous walls are of great technological importance due to their exceptional properties. HOZs contain various layers of porosity, namely mesopores and micropores. Hierarchically ordered zeolites offer advantages over traditional microporous zeolites, for example, by improving the diffusion of guest species to active sites, overcoming steric limitations, improving product selectivity, reducing coke formation, improving hydrothermal stability, and improving the accessibility of Brønsted acid sites and Lewis acid sites; while at the same time, providing improved catalyst performance.

[0009] Numerous synthetic strategies for generating hierarchical zeolites are known and fall into two general categories: bottom-up approaches that involve the use of hard templates and soft templates, and top-down approaches that typically involve post-synthetic treatment. Bottom-up strategies generally involve template formation techniques that are used in situ during zeolite crystallization, for example using a hard template (carbon source) or a soft template (surfactant). Top-down strategies generally involve post-synthetic modification of already formed zeolite crystals, for example by steam formation, dealumination (using an acid), or desilication (using a base). A weakness of known processes for generating hierarchically ordered zeolites is that the long-range ordering of the mesophase in the resulting zeolite is limited or absent, and the mesopores can be random in size, location, and ordering.

[0010] Base-mediated dealumination provides a direct route to creating mesoporosity in highly silica frameworks obtained from steam formation (see, e.g., Verboekend, D., Milina, M., Mitchell, S. & Perez-Ramirez, J. Hierarchical Zeolites by Desilication: Occurrence and Catalytic Impact of Recrystallization and Restructuring. Crys. Growth Des. 13, 5025~(2013)). In particular, integrating organic templates during the dealumination process significantly improves crystallinity and mesoporosity (see, e.g., Garcia-Martinez, J., Johnson, M., Valla, J., Li, K. & Ying, J. Y. Mesostructured Zeolite Y - High Hydrothermal Stability and Superior FCC Catalytic Performance. Catal. Sci. Tech. 2, 987 (2012); Mendoza-Castro, M. J., Serrano, E., Linares, N. & Garcia-Martinez, J. Surfactant-Templated Zeolites: From Thermodynamics to Direct Observation. Adv. Mater. Interfaces 8, 2001388 (2020)). However, such post-synthesis modification strategies typically lack control over dissociation and self-assembly processes, resulting in poorly interconnected mesopores (see, e.g., Schwieger, W. et al., Hierarchy Concepts: Classification and Preparation Strategies for Zeolite Containing Materials with Hierarchical Porosity. Chem. Soc. Rev. 45, 3353~3376, doi:10.1039 / c5cs00599j (2016)).

Prior Art Documents

Patent Documents

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Patent Document 1

Patent Document 2

Patent Document 3

Non-Patent Documents

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Non-Patent Document 1

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Non-Patent Document 4

[0013] In view of conventional attempts to generate hierarchical zeolites, an improved synthesis method is still sought in the art. With respect to these and other problems in the art, the present disclosure is directed to providing a technical solution regarding an effective method for synthesizing and generating hierarchical zeolites having a defined long-range mesoporous order.

Means for Solving the Problems

[0014] A method for synthesizing hierarchical zeolites and zeolite-type materials is provided. The synthesized hierarchical zeolites and zeolite-type materials formed by the methods herein possess a high degree of defined long-range mesoporous order. The method includes base-mediated reassembly by decomposing the parent material to the level of the oligomeric structural building units of the parent material and minimizing or avoiding amorphization / structural collapse. The decomposition and self-assembly are comprehensively controlled to produce hierarchical zeolites and zeolite-type materials by the methods herein.

[0015] In certain embodiments, a method for synthesizing a hierarchical ordered crystalline microporous material is provided, whereby the hierarchical ordered crystalline microporous material has a high degree of long-range mesoporous order. The parent crystalline microporous material (CMM) is subjected to decomposition / cleavage into oligomeric components, which is a reorganization into a hierarchical ordered mesostructure. An effective amount of the parent CMM (having a microporous structure as a basis) is combined with an effective amount of an alkaline reagent and an effective amount of a supramolecular template to form an aqueous suspension. The aqueous suspension is hydrothermally treated under effective conditions to form oligomeric units of the parent CMM, form shaped micelles of the supramolecular template, and induce the assembly of the oligomeric units around the shaped micelles. A solid is formed as a hierarchical ordered mesostructure having a high degree of long-range mesoporous order with pores characterized by crystalline microporous walls that retain the underlying microporous structure.

[0016] In certain embodiments, a method for synthesizing a hierarchically ordered crystalline microporous material is provided. The method includes forming an aqueous suspension by mixing an effective amount of a parent crystalline microporous material having a basal microporous structure, an effective amount of an alkaline reagent, and an effective amount of a supramolecular template; and hydrothermally treating the aqueous suspension under conditions effective for a mesophase transition to break down / cleave the parent crystalline microporous material into oligomeric units of the parent crystalline microporous material, form shaping micelles of the supramolecular template, and reorganize the oligomeric units around the shaping micelles into a hierarchically ordered mesostructure.

[0017] In certain embodiments, the shape of the micelles is adjusted by the selection of the supramolecular template. In certain embodiments, the aqueous suspension further includes an ionic cosolute distinct from the anion associated with the supramolecular template, and the shape of the micelles is adjusted by the selection of the supramolecular template and the ionic cosolute. In certain embodiments, the ionic cosolute is selected from the group consisting of CO3 2- SO4 2- S2O3 2- H2PO4 - F - Cl - Br - NO3 - I - ClO4 - SCN - and C6H5O8 -3 selected from the group consisting of. In certain embodiments, the ionic cosolute is selected from the group consisting of SO4 2- NO3 - and ClO4 - selected from the group consisting of. In certain embodiments, the ionic cosolute includes NO3 - and the hierarchically ordered mesostructure has a cubic mesophase symmetry. In certain embodiments, the ionic cosolute includes SO4 2- and the hierarchically ordered mesostructure has a hexagonal mesophase symmetry. In certain embodiments, the ionic cosolute includes ClO4 -including, the hierarchical ordered mesostructure possesses a lamellar meso symmetry. In certain embodiments, the mesophase transition is characterized by a surfactant packing parameter g, where g = V / a0l, where V is the total volume of the surfactant tails of the supramolecular template, a0 is the area of the head groups of the supramolecular template, and l is the length of the surfactant tails of the supramolecular template. For example: a hierarchical ordered mesostructure possessing a cubic meso symmetry may be characterized by a surfactant packing parameter g in the range of about 0.4 to 0.8; a hierarchical ordered mesostructure possessing a hexagonal meso symmetry may be characterized by a surfactant packing parameter g in the range of about 0.4 to 0.6; and a hierarchical ordered mesostructure possessing a lamellar meso symmetry may be characterized by a surfactant packing parameter g in the range of about 0.9 to 1.1. The amount of ionic cosolute may be expressed as the molar ratio of the cosolute to the supramolecular template. For example: a hierarchical ordered mesostructure possessing a cubic meso symmetry may be characterized by a molar ratio of the cosolute to the supramolecular template in the range of about 0.8 to 1.3; a hierarchical ordered mesostructure possessing a hexagonal meso symmetry may be characterized by a molar ratio of the cosolute to the supramolecular template in the range of about 0.8 to 1.3; and a hierarchical ordered mesostructure possessing a lamellar meso symmetry may be characterized by a molar ratio of the cosolute to the supramolecular template in the range of about 0.2 to 0.7.

[0018] In certain embodiments, the supramolecular template is a bulk surfactant having one or more dimensions larger than the pore dimensions of the crystalline microporous material so as to limit diffusion into the pores of the crystalline microporous material, the dimensions being related to the surfactant head group, the surfactant tail group, or the co-template. In certain embodiments, the supramolecular template contains at least one moiety as a head group or a tail group selected from the group consisting of organosilanes, hydroxysilyls, alkoxysilyls, aromatics, branched alkyls, sulfonates, carboxylates, phosphates, and combinations containing one of the foregoing moieties. In certain embodiments, the supramolecular template contains at least one cationic moiety selected from the group consisting of quaternary ammonium moieties and phosphonium moieties. In certain embodiments, the supramolecular template contains at least one quaternary ammonium group having a terminal alkyl group with 6 to 24 carbon atoms. In certain embodiments, the supramolecular template contains two quaternary ammonium groups, and the alkyl group bridging the quaternary ammonium groups contains 1 to 10 carbon atoms. In certain embodiments, the supramolecular template contains at least one quaternary ammonium group and at least one head group moiety selected from the group consisting of organosilanes, hydroxysilyls, alkoxysilyls, aromatics, branched alkyls, sulfonates, carboxylates, phosphates, and combinations containing one of the foregoing moieties. In certain embodiments, the supramolecular template contains at least one quaternary ammonium group and at least one head group moiety selected from the group consisting of organosilanes, hydroxysilyls, alkoxysilyls, aromatics, branched alkyls, sulfonates, carboxylates, phosphates, and combinations containing one of the foregoing moieties, and the alkyl group bridging at least one of the quaternary ammonium groups and at least one of the head groups contains 1 to 10 atoms. In certain embodiments, the supramolecular template includes dimethyloctadecyl(3-trimethoxysilyl-propyl)-ammonium or a derivative of dimethyloctadecyl(3-trimethoxysilyl-propyl)-ammonium.

[0019] In certain embodiments, the alkaline reagent is provided at a concentration in an aqueous suspension of about 0.1 to 5 wt%, and is selected from the group consisting of ammonia, ammonium hydroxide, and urea. In certain embodiments, the alkaline reagent is urea, and the urea reacts during the hydrothermal treatment to form ammonium hydroxide, thereby controlling the hydrothermal treatment.

[0020] In certain embodiments, the as-formed hierarchical ordered mesostructure is calcined. In certain embodiments, the method reduces the amorphous content of the hierarchical ordered mesostructure.

[0021] In certain embodiments, the parent CMM comprises a zeolite or zeolite-type material. In certain embodiments, the parent CMM comprises a zeolite having a framework selected from the group consisting of AEI, * BEA, CHA, FAU, MFI, MOR, LTL, LTA, and MWW. The parent CMM comprises a zeolite having a FAU framework.

[0022] Any combination of the various embodiments and implementations disclosed herein can be used. These and other aspects and features can be understood from the following description of certain embodiments, the accompanying drawings, and the claims.

[0023] The method of the present disclosure will be described in more detail below with reference to the accompanying drawings in which the same reference numerals are used for the same or similar elements.

Brief Description of the Drawings

[0024]

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Mode for Carrying Out the Invention

[0025] A method for synthesizing hierarchically ordered zeolites and zeolite-type materials (hereinafter, “crystalline microporous material” or “CMM” used in the singular or plural as necessary) is provided. The synthesized hierarchically ordered crystalline microporous material (hereinafter, “HOCMM” used in the singular or plural as necessary) formed by the method herein has a high degree of defined long-range mesoporous order. The HOCMM synthesized in the process herein overcomes the problems associated with known methods by using base-mediated reassembly to decompose the parent CMM to the level of the structural building units that are oligomers of the parent CMM and by minimizing or avoiding amorphization / structural collapse. The CMM decomposition and self-assembly are comprehensively controlled to produce HOCMM by the method herein. The compositions formed by the methods disclosed herein are incorporated herein by reference in their entirety from co-pending and applicant's U.S. Patent Application No. 17 / 857,447, filed July 5, 2022, entitled “Hierarchically Ordered Crystalline Microporous Materials with Long-Range Mesoporous Order Having Cubic Symmetry”; U.S. Patent Application No. 17 / 857,503, filed July 5, 2022, entitled “Hierarchically Ordered Crystalline Microporous Materials with Long-Range Mesoporous Order Having Hexagonal Symmetry”; and U.S. Patent Application No. 17 / 857,572, filed July 5, 2022, entitled “Hierarchically Ordered Crystalline Microporous Materials with Long-Range Mesoporous Order Having Lamellar Symmetry”.

[0026] In certain embodiments of the resynthesis: the rate and extent of CMM degradation are controlled by using urea as a base in situ and by controlling the hydrolysis of urea mediated by the hot water temperature and finely tuning the pH of the solution; the extent of degradation to smaller oligomers is controlled by surfactant-CMM interactions during the initial stages of degradation, whereby the influence of ion-specific interactions, namely the anionic Hofmeister effect (AHE) on supramolecular self-assembly, dictates the formation of hierarchical ordered structures with hexagonal mesopore symmetry, bicontinuous gyroid cubic mesopore symmetry, and lamellar symmetry; in certain embodiments, the hierarchical ordered structures possess hexagonal P6mm mesopore symmetry, bicontinuous gyroid cubic Ia-3d mesopore symmetry, and lamellar p2 symmetry.

[0027] According to an embodiment of the method, the parent CMM is formed in an aqueous suspension by an alkaline reagent and a supramolecular templating agent. In an additional embodiment, the aqueous suspension contains an ionic co-solute as an additional anion distinct from the anion that pairs with the cation of the supramolecular template. The system is maintained under conditions that induce cleavage of the parent CMM into oligomeric units of the CMM with very few monomer units and hierarchical reassembly of those oligomeric units into a mesostructure. The conditions of the system (including the temperature and time of crystallization), the selection and concentration of the supramolecular template, and the selection and concentration of the alkaline reagent are adjusted to control the cleavage of the parent CMM into oligomeric units and the reassembly of those oligomeric units around the shape of the supramolecular template micelle. The degradation of the parent CMM is promoted to an extent of oligomer formation while minimizing monomer formation, which is controlled by the selection of the supramolecular template, the alkaline reagent, the ionic co-solute if necessary, and the hydrothermal conditions (including temperature and time). In certain embodiments, a substantial, significant, or majority portion of the parent CMM is cleaved into oligomeric units, and any remainder thereof takes the form of monomer units or atomic constituents of the CMM. In certain embodiments, the dimensions of the oligomeric units approximately correspond to the synthesized mesoporous structure, the wall thickness of the HOCMM. In certain embodiments, the interfacial curvature of the micelles and oligomeric units under reassembly is adjusted to the desired mesostructure and mesoporosity with the aid of the ionic co-solute and the Hofmeister effect if necessary.

[0028] Under effective crystallization conditions and times, and using an effective type of supramolecular template and alkali reagent at effective relative concentrations, hierarchical ordering by the ensemble occurs after synthesis: the parent CMM is cleaved into oligomeric CMM units that relocate around the shaped micelles formed by the supramolecular template. Hierarchically ordered CMMs with defined long-range mesoporous order are formed by supramolecular templating methods using surfactant micelles. The mesoporous walls are characterized by the parent CMM. Effective supramolecular templates include those having one or more properties that form dimensions that block all, a substantial portion, a significant portion, or most of the supramolecular template molecules from entering the pores, channels, and / or cavities of the parent CMM. These methods disclosed herein cause base-mediated cleavage of CMM crystals into oligomeric components in the presence of a supramolecular template of the type / characteristics disclosed herein, followed by reorganization around defined micelles by supramolecular templating to a hierarchically ordered structure with defined long-range mesoporous order.

[0029] The curvature or shape of the micelles results in the final mesophase symmetry, such as hexagonal, cubic, or lamellar. The formation of micelles from supramolecular template molecules depends on factors such as the type of supramolecular template, the concentration of the supramolecular template, the presence or absence of ionic cosolutes, the type of CMM, the crystallization temperature, the type of alkali reagent, the concentration of the alkali reagent, the pH level of the system, and / or the presence or absence of other reagents. Generally, at low concentrations, the supramolecular template exists as individual entities. At higher concentrations, i.e., above the critical micelle concentration (CMC), micelles are formed. Hydrophobic interactions in systems containing supramolecular templates can change the packing shape of the supramolecular template into, for example, spherical, prolate, or cylindrical micelles, which can then form thermodynamically stable two-dimensional or three-dimensional liquid crystal phases of ordered mesostructures (see, for example, Figure 1.4 of Zana, R. (ed.) (2005), Dynamics of Surfactant Self-Assemblies: Micelles, Microemulsions, Vesicles and Lyotropic Phases (1st ed.). CRC Press, Chapter 1, showing surfactant-based self-assembly and surfactant packing parameters).

[0030] In certain embodiments, the Hofmeister series (HS), ion-specific effects, or lyotropic series are followed for the selection of supramolecular templates and / or ionic co-solutes that control the curvature or shape of micelles (e.g., spheres, ellipsoids, cylinders, or single lamellar structures) (see, e.g., Beibei Kang, Huicheng Tang, Zengdian Zhao, and Shasha Song. “Hofmeister Series: Insights of Ion Specificity from Amphiphilic Assembly and Interface Property” ACS Omega 5 (2020): 6229−6239). In embodiments of methods for synthesizing hierarchical ordered microporous crystalline materials having defined long-range mesoporous order as disclosed herein, the mesophase transitions of the hierarchical ensemble result in distinct mesostructures based on the anionic Hofmeister effect and supramolecular self-assembly. Anions of various sizes and charges carry various polarizabilities, charge densities, and hydration energies in aqueous solutions. When paired with the positive supramolecular template head groups, these properties can affect the short-range electrostatic repulsion within the head groups and the hydration at the micelle interface, and thus change the head group area (a0). Such ion-specific interactions can be the driving force in changing micelle curvature and inducing mesophase transitions. Based on the HS (SO4 2- > HPO4 2- > OAc - > Cl - > Br - > NO3 - > ClO4 - > SCN - ), strongly hydrated ions (left side of the HS) can increase micelle curvature, whereas weakly hydrated ions can decrease micelle curvature. The surfactant packing parameter, g = V / a0l (V = total volume of the surfactant tail, a0 = head group area, l = length of the surfactant tail) can be used to describe these mesophase transitions.

[0031] In the method for synthesizing a hierarchical ordered CMM having a defined long-range mesoporous order disclosed herein, the appropriate alkaline reagent comprises one or more basic compounds to maintain the system at a pH level greater than about 8. In certain embodiments, the alkaline reagent is provided at a concentration in an aqueous suspension of about 0.1 - 2.0 M. In certain embodiments, the alkaline reagent is provided at a concentration in an aqueous suspension of about 0.1 - 5 wt%. In certain embodiments, the alkaline reagent comprises urea. In certain embodiments, the alkaline reagent comprises ammonia. In certain embodiments, the alkaline reagent comprises ammonium hydroxide. In certain embodiments, the alkaline reagent comprises sodium hydroxide. In certain embodiments, the alkaline reagent comprises an alkali metal hydroxide comprising a hydroxide of sodium, lithium, potassium, rubidium, or cesium.

[0032] In certain embodiments, the alkaline reagent is effective to enable controlled hydrolysis; for example, urea can be used as an alkaline agent and during hydrolysis, urea reacts to form ammonium hydroxide. For example, a higher urea concentration can be used in the initial step and the basicity can be maintained by stepwise hydrolysis of urea. In such embodiments, the pH increases relatively slowly to the maximum pH as a function of time rather than adding some amount of another alkaline reagent such as ammonium hydroxide to the initial solution towards the maximum pH, which is beneficial for the process. Unlike conventional bases that act quickly, urea has a neutral pH under ambient conditions and can be uniformly dispersed throughout the zeolite micropores without affecting them.

[0033] In certain embodiments, the alkaline reagent comprises an alkylammonium cation having the general formula R X H 4-X N + [A - , where X = 1 - 4, R1, R2, R3, and R4 are the same or various C1 - C30 alkyl groups, and [A - is OH - , Br - , Cl- or I - is a counter anion that can be used. In certain embodiments, the alkali reagent includes a quaternary ammonium cation having an alkoxysilyl group, a phosphonium group, an alkyl group, an alkyl group with a bulkier substituent, or an alkoxyl group with a bulkier substituent. In certain embodiments, the alkylammonium cation used in this regard functions as a base rather than a surfactant or a template.

[0034] In certain embodiments where ammonia, ammonium hydroxide, or an alkali metal hydroxide is used, amorphous material is also present in the product along with crystalline material. In certain embodiments, by calcining the as-made HOCMM, the amount of obvious amorphous material present is reduced (e.g., a broad band overall at 25° (2θ) in XRD), which indicates an obvious "self-healing" after calcination. In certain embodiments, when directly compared with an alternative route such as NaOH or ammonium hydroxide, the amount of obvious amorphous material present in HOCMM is reduced by the controlled hydrolysis of urea to ammonium hydroxide (e.g., a broad band overall at 25° (2θ) in XRD).

[0035] In a method for synthesizing a hierarchical ordered CMM having a defined long-range mesoporous order disclosed herein, a suitable surfactant is provided as a supramolecular template to assist in the reassembly and recrystallization of decomposition components (oligomers) by means of shared and / or electronic valence interactions. The supramolecular template is provided at a concentration in an aqueous suspension of about 0.01 to 0.5 M. In certain embodiments, a suitable supramolecular template is provided at a concentration in an aqueous suspension of about 0.5 to 10 wt%. A suitable supramolecular template is characterized by restricted diffusion in the micropore channels of the parent CMM, called bulk surfactant or bulk supramolecular template. Diffusion of the supramolecular template molecules into the micropore-channels or cavities promotes CMM decomposition. This is minimized in the top-down method for synthesizing a hierarchical ordered CMM having a defined long-range mesoporous order disclosed herein, and its effective supramolecular template minimizes or suppresses diffusion or partial diffusion into the CMM pore-channels, cavities, or window openings. Such a supramolecular template has dimensions suitable for blocking such diffusion. Suitable dimensions can be based on the dimensions of the head group and / or tail group of the supramolecular template. In certain embodiments, suitable dimensions can be based on a co-template having one or more components with stable head and / or tail groups, or can be a template system arranged and configured in such a way as to minimize or block diffusion into the CMM pore-channels, cavities, or window openings. By minimizing the diffusion of the template into the CMM pore channels, CMM decomposition into oligomers, as well as the comprehensive reorganization and assembly into a hierarchical ordered CMM having a defined long-range mesoporous order disclosed herein, are promoted. In certain embodiments, the supramolecular template is one in which at least a substantial portion, a significant portion, or a majority of the surfactant does not enter into the pores and / or channels of the CMM. For example, organosilane (about 0.7 nm) is relatively large compared to a quaternary ammonium surfactant having no such bulk group, including cetyltrimethylammonium bromide (CTAB) (about 0.25 nm).In certain embodiments, the supramolecular template contains a long-chain linear group (> about 0.6 nm). In certain embodiments, the supramolecular template contains an aromatic or aromatic derivative group (> about 0.6 nm). In certain embodiments, the supramolecular template contains one or more bulk-like groups having dimensions based on modeling the molecular dimensions as a rectangular parallelepiped having dimensions A, B, and C using the van der Waals radius for each individual atom, and one or more, two or more, or all three of dimensions A, B, and C are of a size sufficiently close or large enough to restrict diffusion into the micropores of the selected parent CMM.

[0036] In certain embodiments, the surfactant effective as a supramolecular template contains at least one moiety as a head group or a tail group selected from the group consisting of organosilanes, hydroxysilyls, alkoxysilyls, aromatics, branched alkyls, sulfonates, carboxylates, phosphates, and combinations containing one of the foregoing moieties. In certain embodiments, the effective supramolecular template is an organosilane containing at least one hydroxysilyl as a head group moiety. In certain embodiments, the effective supramolecular template is an organosilane containing at least one hydroxysilyl as a tail group moiety. In certain embodiments, the effective supramolecular template is an organosilane containing at least one alkoxysilyl as a head group moiety. In certain embodiments, the effective supramolecular template is an organosilane containing at least one alkoxysilyl as a tail group moiety. In certain embodiments, the effective supramolecular template contains at least one aromatic as a head group moiety. In certain embodiments, the effective supramolecular template contains at least one aromatic as a tail group moiety. In certain embodiments, the effective supramolecular template contains at least one branched alkyl as a head group moiety. In certain embodiments, the effective supramolecular template contains at least one branched alkyl as a tail group moiety. In certain embodiments, the effective supramolecular template contains at least one sulfonate as a head group moiety. In certain embodiments, the effective supramolecular template contains at least one sulfonate as a tail group moiety. In certain embodiments, the effective supramolecular template contains at least one carboxylate as a head group moiety. In certain embodiments, the effective supramolecular template contains at least one carboxylate as a tail group moiety. In certain embodiments, the effective supramolecular template contains at least one phosphate as a head group moiety. In certain embodiments, the effective supramolecular template contains at least one phosphate as a tail group moiety. These moieties are characterized by one or more dimensions that limit diffusion into the pores of the parent CMM.In certain embodiments where the CMM is characterized by pores of various dimensions, the selected portion is characterized by one or more dimensions that limit diffusion into the largest pores of the parent CMM.

[0037] In certain embodiments, an effective supramolecular template contains at least one cationic moiety. In certain embodiments, an effective supramolecular template contains at least one cationic moiety selected from the group consisting of quaternary ammonium moieties and phosphonium moieties. In certain embodiments, an effective supramolecular template contains at least one quaternary ammonium group having a terminal alkyl group with 6 to 24 carbon atoms. In certain embodiments, an effective supramolecular template contains two quaternary ammonium groups, and the alkyl group bridging the quaternary ammonium groups contains 1 to 10 carbon atoms. In certain embodiments, an effective supramolecular template contains at least one quaternary ammonium group, and at least one constituent moiety, the head group moiety described above. In certain embodiments, an effective supramolecular template contains at least one quaternary ammonium group, and at least one constituent moiety, the tail group moiety described above. In certain embodiments, an effective supramolecular template contains at least one quaternary ammonium group, at least one constituent moiety, the head group moiety described above, and an alkyl group containing 1 to 10 carbon atoms that bridges at least one of the at least one quaternary ammonium group and at least one of the head groups. In certain embodiments, an effective supramolecular template contains at least one quaternary ammonium group, at least one constituent moiety, the tail moiety described above, and an alkyl group containing 1 to 10 carbon atoms that bridges at least one of the at least one quaternary ammonium group and at least one of the tail groups.

[0038] In certain embodiments, an effective supramolecular template comprises a quaternary ammonium compound and a structural group comprising one or more bulk organic silanes or alkoxysilyl substituents. In certain embodiments, an effective supramolecular template comprises a quaternary ammonium compound and a structural group comprising one or more long-chain organic silanes or alkoxysilyl substituents. In certain embodiments, an effective supramolecular template cation comprises dimethyloctadecyl(3-trimethoxysilyl-propyl)-ammonium, or a derivative of dimethyloctadecyl(3-trimethoxysilyl-propyl)-ammonium. In certain embodiments, an effective supramolecular template cation comprises dimethylhexadecyl(3-trimethoxysilyl-propyl)-ammonium, or a derivative of dimethylhexadecyl(3-trimethoxysilyl-propyl)-ammonium. In certain embodiments, an effective supramolecular template cation comprises a double-acyl-oxy amphiphilic organic silane, such as [2,3-bis(dodecanoyloxy)-propyl](3-(trimethoxysilyl)propyl)-dimethylammonium, or a derivative of [2,3-bis(dodecanoyloxy)-propyl](3-(trimethoxysilyl)propyl)-dimethylammonium.

[0039] In certain embodiments, an effective supramolecular template comprises a quaternary phosphonium compound and a structural group comprising one or more bulk aromatic substituents. In certain embodiments, an effective supramolecular template comprises a quaternary phosphonium compound and a structural group comprising one or more bulk alkoxysilyl or organic silane substituents.

[0040] In certain embodiments, an effective supramolecular template contains a tail group portion selected from the group consisting of an aromatic group containing from 6 to 50, 6 to 25, 10 to 50, or 10 to 25 carbon atoms, an alkyl group containing from 1 to 50, 1 to 25, 5 to 50, 5 to 25, 10 to 50, or 10 to 25 carbon atoms, an aryl group containing from 1 to 50, 1 to 25, 5 to 50, 5 to 25, 10 to 50, or 10 to 25 carbon atoms, or a combination of aromatic and alkyl groups having up to 50 carbon atoms. In certain embodiments, an effective supramolecular template contains a head group portion selected from the group consisting of an aromatic group containing from 6 to 50, 6 to 25, 10 to 50, or 10 to 25 carbon atoms, an alkyl group containing from 1 to 50, 1 to 25, 5 to 50, 5 to 25, 10 to 50, or 10 to 25 carbon atoms, an aryl group containing from 1 to 50, 1 to 25, 5 to 50, 5 to 25, 10 to 50, or 10 to 25 carbon atoms, or a combination of aromatic and alkyl groups having up to 50 carbon atoms. In certain embodiments, an effective supramolecular template contains a co-templating agent selected from the group consisting of quaternary ammonium compounds (e.g., including quaternary alkylammonium cation species) and quaternary phosphonium compounds.

[0041] In certain embodiments, an effective supramolecular template is: (a) at least one of an aromatic quaternary ammonium compound, a branched alkyl chain quaternary ammonium compound, an alkylbenzene sulfonate, an alkylbenzene phosphonate, an alkylbenzene carboxylate, or a substituted phosphonium cation; and (b1) a constituent group containing at least one of an organosilane, a hydroxysilyl, an alkoxysilyl, an aromatic, a branched alkyl, a sulfonate, a carboxylate, or a phosphate as a head group; or (b2) a constituent group containing at least one of an organosilane, a hydroxysilyl, an alkoxysilyl, an aromatic, a branched alkyl, a sulfonate, a carboxylate, or a phosphate as a tail group. In certain embodiments, an effective supramolecular template contains a sulfonate group (non-limiting examples include sulfonated bis(2-hydroxy-5-dodecylphenyl)methane (SBHDM)). In certain embodiments, an effective supramolecular template contains a carboxylate group (non-limiting example is sodium 4-(octyloxy)benzoate). In certain embodiments, an effective supramolecular template contains a phosphonate group (non-limiting example is tetradecyl(1,4-benzene)bisphosphonate). In certain embodiments, an effective supramolecular template contains an aromatic group (non-limiting example is cetyl dimethyl benzyl ammonium chloride). In certain embodiments, an effective supramolecular template contains an aliphatic group (non-limiting example is tetraoctylammonium chloride).

[0042] The supramolecular template is provided as a cation / anion pair. In certain embodiments, the cation of the supramolecular template is as described above, and Cl - 、Br - 、OH - 、F - 、and I - and other selected anions pair therewith. In certain embodiments, the cation of the supramolecular template is as described above, and Cl - 、Br - 、or OH -It pairs with anions such as. In certain embodiments, an effective supramolecular template includes dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (commonly abbreviated as "TPOAC"), or a derivative of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride. In certain embodiments, an effective supramolecular template includes dimethylhexadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, or a derivative of dimethylhexadecyl[3-(trimethoxysilyl)propyl]ammonium chloride. In certain embodiments, an effective supramolecular template includes [2,3-bis(dodecanoyloxy)-propyl](3-(trimethoxysilylpropyl)-dimethylammonium iodide, or a derivative of [2,3-bis(dodecanoyloxy)-propyl](3-(trimethoxysilylpropyl)-dimethylammonium iodide).

[0043] In certain embodiments, the system includes an effective amount of an ionic cosolute (i.e., in addition to the anion paired with the supramolecular template). In certain embodiments where an ionic cosolute is used, it is provided at a concentration in an aqueous suspension of about 0.01 - 0.5 M. In certain embodiments where an ionic cosolute is used, it is provided at a concentration in an aqueous suspension of about 0.01 - 5 wt%. In certain embodiments, the ionic cosolute is selected from the group consisting of CO3 2- SO4 2- S2O3 2- H2PO4 - F - Cl - Br - NO3 - I - ClO4 - SCN - and C6H5O8 -3 (citrate). In certain embodiments, the ionic cosolute is SO4 2- NO3 - and ClO4 -selected from the group consisting of. In certain embodiments, the ionic cosolute is selected based on the Hofmeister series / lyotropic series to control the curvature / shape of the micelles to provide a desired mesophase symmetry, such as hexagonal, cubic, or lamellar. In certain embodiments, nitrate (NO3 - ) is an ionic cosolute selected based on the Hofmeister series / lyotropic series to control the curvature / shape of the micelles to provide a hierarchical ordered CMM with a defined long-range mesoporous order having a cubic mesophase symmetry; in certain embodiments where nitrate is used as the ionic cosolute, nitrates such as ammonium nitrate or metal nitrates are used, and this metal can be an alkali metal, alkaline earth metal, transition metal, noble metal, or rare earth metal. In certain embodiments, sulfate (SO4 2- ) is an ionic cosolute selected based on the Hofmeister series / lyotropic series to control the curvature / shape of the micelles to provide a hierarchical ordered CMM with a defined long-range mesoporous order having a hexagonal mesophase symmetry; in certain embodiments, sulfate is used as the ionic cosolute, and sulfates such as ammonium sulfate or metal sulfates are used, and this metal can be an alkali metal, alkaline earth metal, transition metal, noble metal, or rare earth metal. In certain embodiments, perchlorate (ClO4 - ) is an ionic cosolute selected based on the Hofmeister series / lyotropic series to control the curvature / shape of the micelles to provide a hierarchical ordered CMM with a defined long-range mesoporous order having a lamellar mesophase symmetry; in certain embodiments, perchlorate is used as the ionic cosolute, and sulfates such as sodium perchlorate or another metal perchlorate are used, and this metal can be an alkali metal, alkaline earth metal, transition metal, noble metal, or rare earth metal.

[0044] The present disclosure is applicable to various types of CMMs as parent materials, including zeolites or zeolite-type materials. In certain embodiments, the parent CMM exhibits both good crystallinity and Al distribution in order to obtain a high-quality HOCMM while maintaining composite phases and / or impurities.

[0045] Zeolite materials suitable as parent CMMs are the identifiers ABW, ACO, AEI, AEL, AEN, AET, AFG, AFI, AFN, AFO, AFR, AFS, AFT, AFV, AFX, AFY, AHT, ANA, ANO, APC, APD, AST, ASV, ATN, ATO, ATS, ATT, ATV, AVE, AVL, AWO, AWW, BCT, BEC, BIK, BOF, BOG, BOZ, BPH, BRE, BSV, CAN, CAS, CDO, CFI, CGF, CGS, CHA, -CHI, -CLO, CON, CSV, CZP, DAC, DDR, DFO, DFT, DOH, DON, EAB, EDI, EEI, EMT, EON, EPI, ERI, ESV, ETL, ETR, ETV, EUO, EWO, EWS, EZT, FAR, FAU, FER, FRA, GIS, GIU, GME, GON, GOO, HEU, IFO, IFR, -IFT, -IFU, IFW, IFY, IHW, IMF, IRN, IRR, -IRY, ISV, ITE, ITG, ITH, ITR, ITT, -ITV, ITW, IWR, IWS, IWV, IWW, JBW, JNT, JOZ, JRY, JSN, JSR, JST, JSW, KFI, LAU, LEV, LIO, -LIT, LOS, LOV, LTA, LTF, LTJ, LTL, LTN, MAR, MAZ, MEI, MEL, MEP, MER, MFI, MFS, MON, MOR, MOZ, MRT, MSE, MSO, MTF, MTN, MTT, MTW, MVY, MWF, MWW, NAB, NAT, NES, NON, NPO, NPT, NSI, OBW, OFF, OKO, OSI, OSO, OWE, -PAR, PAU, PCR, PHI, PON, POR, POS, PSI, PTO, PTT, PTY, PUN, PWN, PWO, PWW, RHO, -RON, RRO, RSN, RTE, RTH, RUT, RWR, RWY, SAF, SAO, SAS, SAT, SAV, SBE, SBN, SBS, SBT, SEW, SFE, SFF, SFG, SFH, SFN, SFO, SFS, SFW, SGT, SIV, SOD, SOF, SOR, SOS, SOV, SSF, SSY, STF, STI, STT, STW, -SVR, SVV, SWY, -SYT, SZR, TER, THO, TOL, TON, TSC, TUN, UEI, UFI, UOS, UOV, UOZ, USI, UTL, UWY, VET, VFI, VNI, VSV, WEI, -WEN,YFI, YUG, ZON, * BEA, * CTH, * -EWT, * -ITN, * MRE, * PCS, * SFV, * -SSO, * STO, * -SVY, and * including those having UOE, including those identified by the International Zeolite Association. For example, certain zeolites known to be useful in the petroleum refining industry include, but are not limited to, AEI, * BEA, CHA, FAU, MFI, MOR, LTL, LTA, or MWW. In certain embodiments, the parent zeolite can be a (FAU) framework zeolite including, for example, USY having a micropore diameter related to a 12-membered ring as viewed along the

[0111] direction of, for example, 7.4×7.4 Å. In certain embodiments, the parent zeolite can be a (MFI) framework zeolite including, for example, ZSM-5 having micropore diameters related to 10-membered rings as viewed along the

[0100] and

[0010] directions of, respectively, 5.5×5.1 Å and 5.6×5.3 Å. In certain embodiments, the parent zeolite can be a (MOR) framework zeolite including, for example, mordenite zeolite having micropore diameters related to 12-membered and 8-membered rings as viewed along the

[0001] and

[0001] directions of, respectively, 6.5×7.0 Å and 2.6×5.7 Å. In certain embodiments, the parent zeolite can be, for example, zeolite beta polymorph A having a micropore diameter related to a 12-membered ring as viewed along the

[0100] and

[0001] directions of, respectively, 6.6×6.7 Å and 5.6×5.6 Å, ( *BEA) It can be a framework zeolite. In certain embodiments, the parent zeolite can be a (CHA) framework zeolite, including, for example, chabazite zeolite having a micropore diameter related to an 8-membered ring when viewed perpendicular to the

[0001] direction, such as 3.8×3.8 Å. In certain embodiments, the parent zeolite can be a (LTL) framework zeolite, including, for example, Linde type L zeolite (zeolite L) having a micropore diameter related to a 12-membered ring when viewed along the

[0001] direction, such as 7.1×7.1 Å. In certain embodiments, the parent zeolite can be a (LTA) framework zeolite, including, for example, Linde type A zeolite (zeolite A) having a micropore diameter related to an 8-membered ring when viewed along the

[0100] direction, such as 4.1×4.1 Å. In certain embodiments, the parent zeolite can be an (AEI) framework zeolite having a micropore diameter related to an 8-membered ring when viewed perpendicular to the

[0001] direction, such as 3.8×3.8 Å. In certain embodiments, the parent zeolite can be a (MWW) framework zeolite, including, for example, MCM-22 having micropore diameters related to 10-membered rings of 4.0×5.5 Å and 4.1×5.1 Å respectively for the "interlayer" and "intralayer" when viewed perpendicular to the

[0001] direction.

[0046] In certain embodiments, the parent CMM is a zeolite-type material, such as aluminophosphate (AlPO), silicon-substituted aluminophosphate (SAPO), or metal-containing aluminophosphate (MAPO). In certain embodiments, the parent CMM is a framework material containing only silicon in the zeolite system.

[0047] As described above, embodiments of the present specification include a supramolecular template containing one or more bulk-like groups having dimensions based on modeling of molecular dimensions as a rectangular parallelepiped having dimensions A, B, and C that use the van der Waals radius for each individual atom, wherein one or more, two or more, or all three of dimensions A, B, and C have dimensions that are sufficiently close or sufficiently large such that they limit diffusion into the micropores of the CMM. Also, as already described with respect to known parameters related to pore dimensions for exemplary zeolites, such parameters affect the selection of the supramolecular template. For example, in the examples herein, FAU zeolite was used; when the supramolecular template material was CTAB (about 0.25 nm), HOCMM was not achieved; however, when the supramolecular template was an organosilane (about 0.7 nm), HOCMM was achieved because these dimensions are close to the pore dimensions of the FAU zeolite and thus diffusion into such pores is restricted. Similarly, a suitable supramolecular template is determined based on the selected parent CMM.

[0048] In certain embodiments, the parent CMM used in the method is a zeolite of the present specification having an SAR suitable for a particular type of zeolite. Generally, the SAR of the parent zeolite can range from about 2 to 10000, 2 to 5000, 2 to 500, 2 to 100, 2 to 80, 5 to 10000, 5 to 5000, 5 to 500, 5 to 100, 5 to 80, 10 to 10000, 10 to 5000, 10 to 500, 10 to 100, 10 to 80, 50 to 10000, 50 to 5000, 50 to 1000, 50 to 500, or 50 to 100. In certain embodiments, the SAR of the parent zeolite is greater than or equal to 5 or 10 to achieve long-range order. In embodiments where the SAR is less than 10, uniform mesoporosity and a certain degree of order can be achieved and the amorphous framework material remains in the product.

[0049] Synthesis process Figures 1 and 2 are schematic diagrams of the hierarchical order by the post-synthesis ensemble synthesis route described herein, including the schematic synthesis mechanism for changing the curvature of micelles and inducing mesophase transitions and how AHE affects the g value therefor. The CMMs schematically shown in Figures 1 and 2 are FAU zeolites, but it is understood that other CMMs can be used as the parent CMM by the post-synthesis ensemble synthesis route.

[0050] The method includes base-mediated decomposition / cleavage of the parent CMM into oligomeric components and reorganization into a hierarchical ordered mesostructure by supramolecular templating and, in certain embodiments, by the Hofmeister effect. The parent CMM 10 is provided in a crystalline form. An effective amount of an alkaline reagent and an effective amount of a surfactant are added for supramolecular templating to form an aqueous suspension, and the suspension is maintained under hydrothermal conditions to form oligomeric CMM units 12 of the parent CMM (such as oligomeric zeolite units when the parent CMM is a zeolite). The supramolecular template molecules 14 are formed in the shaped micelles 16 (not shown in Figure 2), and the oligomeric CMM units hierarchically reassemble and crystallize around the shaped micelles into an ordered mesostructure, HOCMM 18, having defined symmetric mesopores 20 and mesopore walls formed of the oligomeric CMM units, thereby retaining the micropores 22 of the CMM structure underlying the parent CMM. In certain embodiments, the composition produced by the method herein is the HOCMM 18 containing the shaped micelles 16. In certain embodiments, the composition produced herein is the HOCMM 18 having the surfactant 14 formed in the shaped micelles 16 removed by chemical methods such as, for example: solvent extraction, chemical oxidation, or ionic liquid treatment; or physical methods such as calcination, supercritical CO2, microwave-assisted treatment, ultrasonic-assisted treatment, ozone treatment, or plasma technology.

[0051] The distinct mesophase transitions of hierarchical assemblies that result in distinct mesostructures may be due to the synergistic action of the anionic Hofmeister effect (ion-specific interactions) in supramolecular self-assembly. Anions of various sizes and charges possess various polarizabilities, charge densities, and hydration energies in aqueous solution. When paired with the positive surfactant head groups, these properties can affect the electrostatic repulsion between the head groups and the hydration of the micelle interface, thus changing the head group area (a0). Such short-range ion-specific interactions can be a significant driving force in changing the curvature of micelles and inducing mesophase fibers.

[0052] Referring to FIG. 2, a schematic synthesis mechanism is shown that includes a schematic representation of how AHE affects the g-value to change the curvature of the micelles and induce a mesophase transition. The molar ratio of the surfactant (also referred to herein as the supramolecular template) to the cosolute (which may be expressed as the molar ratio to the salt of the surfactant) is effective for generating the desired mesophase structure. The molar ratio of the surfactant to the cosolute is selected to provide a surfactant packing parameter suitable for inducing a mesophase transition to a desired geometry that induces a change in the curvature of the micelles. For example, when sulfate is used as the ionic cosolute, the curvature of the micelles is represented as a surfactant packing parameter g of about 1 / 2 or about 0.4 - 0.6 or 0.5, and the resulting HOCMM has a hexagonal symmetric long-range mesoporous order. When nitrate is used as the ionic cosolute, the curvature of the micelles is represented by a surfactant packing parameter g in the range from about 1 / 2 to about 2 / 3, or in the range of about 0.4 - 0.8, 0.4 - 0.67, 0.5 - 0.8, or 0.5 - 0.67, and the resulting HOCMM has a cubic symmetric long-range mesoporous order. When perchlorate is used as the ionic cosolute, the curvature of the micelles is represented as a surfactant packing parameter g in the range of about 0.9 - 1.1 or 1, and the resulting HOCMM has a lamellar symmetric long-range mesoporous order. For example, in certain embodiments, the molar ratio of the surfactant to the cosolute for synthesizing an HOCMM having a hexagonal symmetric long-range mesoporous order may be in the range of about 0.8 - 1.3, 0.9 - 1.3, 0.9 - 1.2, or 0.8 - 1.2. For example, in certain embodiments, the molar ratio of the surfactant to the cosolute for synthesizing an HOCMM having a cubic symmetric long-range mesoporous order may be in the range of about 0.8 - 1.3, 0.9 - 1.3, 0.9 - 1.2, or 0.8 - 1.2. For example, in certain embodiments, the molar ratio of the surfactant to the cosolute for synthesizing an HOCMM having a lamellar symmetric long-range mesoporous order may be in the range of about 0.2 - 0.7, 0.3 - 0.7, 0.2 - 0.6, or 0.3 - 0.6.Even broader ranges as listed in this specification may be applicable, and it is understood that these ranges can vary depending on the selected surfactant and cosolute, which affect the values of V (total volume of surfactant tails), a0 (area of the head group), and l (length of the surfactant tails) for determining g (surfactant packing parameter). In certain embodiments, the range of the surfactant packing parameter g and / or the range of the molar ratio of the surfactant to the cosolute are effective for organic silane supramolecular templates such as dimethyloctadecyl(3 - trimethoxysilyl - propyl)-ammonium or derivatives of dimethyloctadecyl(3 - trimethoxysilyl - propyl)-ammonium.

[0053] Figure 2 also shows the effect of ion - specific interactions (the Hofmeister effect) on the curvature of micelles in the self - assembly process. Anions of various sizes and charges carry various polarizabilities, charge densities, and hydration energies in aqueous solutions. When paired with the positive surfactant head groups, these properties can affect the electrostatic repulsion between the head groups and the hydration at the micelle interface, and thus change the area of the head group (a0). Such short - range ion - specific interactions can be a significant driving force in changing micelle curvature and inducing mesophase transitions. The Hofmeister series (SO4 2- > HPO4 2- > OAc - > Cl - > Br - > NO3 - > ClO4 - > SCN -Based on , strongly hydrated ions (on the left side of the series) can increase the micelle curvature, while weakly hydrated ions can reduce the micelle curvature. Without being bound by theory, the influence of cosolutes such as salts in the mesophase order may be due to its charge balancing effect; in surfactant self-assembly, due to the hydrophobic effect, high-density surfactant molecules are tightly packed within the micelle; as a result, the electrostatic repulsion of the charged head groups should be minimized by counteranions to induce easy aggregation; thus, the auxiliary counteranions play a role in stabilizing the micelle despite the stepwise change in the concentration of the polyanionic zeolite component.

[0054] An effective amount of solvent is used in the process. In certain embodiments, the solvent is water. In certain embodiments, the solvent is water in the presence of a cosolvent selected from the group consisting of polar solvents, nonpolar solvents, and pore swelling agents (such as 1,3,5-trimethylbenzene). In certain embodiments, the solvent is selected from the group consisting of polar solvents, nonpolar solvents, and pore swelling agents (such as 1,3,5-trimethylbenzene) in the absence of water. In an embodiment, the mixture components are added to the reaction vessel together with water and then heated. Typically, water allows for proper mixing to achieve a more homogeneous distribution of the suspension components and ultimately results in a more desirable product as the properties of each crystal match more closely with the adjacent crystals. Insufficient mixing may lead to undesirable products with an amorphous phase or a lower degree of long-range order.

[0055] The suspension components are combined in any suitable order and thoroughly mixed to form a homogeneous distribution of the suspension components. The suspension can be maintained under autogenous pressure (from the components or with the addition of a gas purge into the tank before heating the components), in an autoclave, or in another suitable tank with stirring, tumbling, and / or shaking, etc. The mixing of the suspension components is carried out between about 20 - 60, 20 - 50, or 20 - 40 °C.

[0056] The cutting and reassembly steps are carried out during the hydrothermal treatment to form solids (product, HOCMM with defined long-range mesoporous order) suspended in the supernatant (mother liquor). The hydrothermal treatment is carried out over a period of about 4 to 168, 12 to 168, 24 to 168, 4 to 96, 12 to 96, or 24 to 96 hours; at a temperature of about 70 to 250, 70 to 210, 70 to 180, 70 to 160, 70 to 150, 90 to 250, 90 to 210, 90 to 180, 90 to 160, 90 to 150, 110 to 250, 110 to 210, 110 to 180, 110 to 160, or 110 to 150 °C; and at a pressure from approximately atmospheric pressure to autogenous pressure. In certain embodiments, the hydrothermal treatment is carried out in the same tank as that used for mixing, or the suspension is transferred to another tank (such as another autoclave or low-pressure tank). In certain embodiments, the tank used for the hydrothermal treatment is stationary. In certain embodiments, the tank used for the hydrothermal treatment is in a stirring state sufficient to suspend the components.

[0057] The HOCMM with defined long-range mesoporous order is the product to be recovered. The solids are recovered using known techniques such as centrifugation, decantation, gravity, vacuum filtration, filter press, or rotary drum. The recovered HOCMM with defined long-range mesoporous order is dried at a temperature of, for example, about 50 to 150, 50 to 120, 80 to 150, or 80 to 120 °C under atmospheric or vacuum conditions for a period of about 0.5 to 96, 12 to 96, or 24 to 96 hours.

[0058] In certain embodiments, the dried HOCMM having a defined long-range mesoporous order is calcined to remove, for example, the mesophase supramolecular template and other constituents from the mesopores and / or the individual zeolite cell micropores. The conditions for calcination of the embodiments implemented can include a temperature in the range of about 350 - 650, 350 - 600, 350 - 550, 500 - 650, 500 - 600, or 500 - 550 °C, under atmospheric pressure or vacuum, and a period of about 2.5 - 24, 2.5 - 12, 5 - 24, or 5 - 12 hours. The calcination can be carried out at a rate of increase in the range of about 0.1 - 10, 0.1 - 5, 0.1 - 3, 1 - 10, 1 - 5, or 1 - 3 °C per minute. In certain embodiments, the calcination can have a first step of raising the temperature to between 100 - 150 °C and having a holding time of about 1.5 - 6 or 1 - 12 hours (the rate of increase is about 0.1 - 5, 0.1 - 3, 1 - 5, or 1 - 3 °C per minute), and then raising to a higher temperature and having a final holding time in the range of about 1.5 - 6 or 1 - 12 hours.

[0059] In certain embodiments, the supernatant remaining after recovering the product from the system can be recovered and all or a portion thereof can be reused as all or a portion of the solution in subsequent processes for synthesizing a HOCMM having a defined long-range mesoporous order. In this embodiment, the recovered supernatant used in the subsequent process is referred to as the supernatant from a conventional synthesis. In certain embodiments, the new synthesis can be performed using the supernatant from a conventional synthesis together with the parent CMM. In certain embodiments, the new synthesis can be performed using the supernatant from a conventional synthesis together with the parent CMM and an additional amount of a constituent alkaline reagent (e.g., urea). In certain embodiments, the new synthesis can be performed using the supernatant from a conventional synthesis together with the parent CMM and an additional amount of a constituent supramolecular template. In certain embodiments, the new synthesis can be performed using the supernatant from a conventional synthesis together with the parent CMM and an additional amount of a constituent ionic cosolute. In certain embodiments, the new synthesis can be performed using the supernatant from a conventional synthesis together with the parent CMM and an additional amount of a constituent alkaline reagent (e.g., urea) and / or a constituent supramolecular template and / or a constituent ionic cosolute as needed.

[0060] product The compositions recovered as described herein are hierarchical ordered CMMs (such as zeolites) having a defined long-range mesoporous order. These are characterized by the mesoporous channel direction defined by the zeolite micropore channels within the walls of the mesostructure. The HOCMMs having a defined long-range mesoporous order, recovered from synthesis, carry within their mesopores (i.e., prior to calcination or extraction of the supramolecular template) the supramolecular templates described herein. In certain embodiments, the HOCMMs having a defined long-range mesoporous order, recovered from synthesis, carry within their mesopores (i.e., prior to calcination or extraction of the supramolecular template) micelles of the supramolecular templates described herein. The recovered compositions described herein retain the structural integrity of the microporous zeolite structure by controlled cleavage of the parent zeolite and subsequent controlled reassembly of the zeolite oligomers under controlled micelle curvature, resulting in HOCMMs with a defined mesoporous symmetry.

[0061] This defined long-range mesoporosity is difficult to understand in the field of hierarchical ordered zeolites. The long-range order is defined by secondary peaks associated with the periodic arrangement of mesopores in the x-ray diffraction (XRD) pattern for a given mesophase, as demonstrated in the examples herein, and / or by microscopic observation. These peaks associated with the mesoporous characteristics of the product are observed at low 2θ angles. The material also shows high angle peaks associated with the zeolite and is observed at high 2-theta angles. In certain embodiments, the low angle peaks refer to those occurring at 2θ angles of less than about 6°.

[0062] In certain embodiments herein, the long-range mesoporous order of the HOCMMs produced by the methods described herein is characterized by the periodicity of mesopores repeating over lengths greater than about 50 nm.

[0063] In certain embodiments of the present specification, the HOCMM generated by the method described herein is a cubic mesophase having Ia-3d symmetry, and the long-range mesoporous order is characterized by secondary XRD peaks associated with the periodic arrangement of mesopores present in one or more of the (220), (321), (400), (420), and (332) reflections. In certain embodiments of the present specification, the HOCMM generated by the method described herein is a hexagonal mesophase having p6mm symmetry, and the long-range mesoporous order is characterized by secondary peaks of XRD present in the (11) and / or (20) reflections. In certain embodiments of the present specification, the HOCMM generated by the method described herein is a lamellar mesophase having p2 symmetry, and the long-range mesoporous order is characterized by secondary peaks of XRD present in the (200) reflection.

[0064] In certain embodiments of the present specification, the HOCMM having a defined long-range mesoporous order generated by the method described herein is about 200 - 1500, 200 - 1000, 200 - 900, 400 - 1500, 400 - 1000, 400 - 900, 500 - 1500, 500 - 1000, or 500 - 900 m 2It has a surface area of / g. In the embodiments of the present specification, the HOCMM having a defined long-range mesoporous order generated by the method described in the present specification has a mesoporous pore diameter of about 2 to 50, 2 to 20, or 2 to 10 nm. In the embodiments of the present specification, the HOCMM having a defined long-range mesoporous order generated by the method described in the present specification has a silica-to-alumina ratio of about 2.5 to 1500, 3 to 1500, 4 to 1500, 5 to 1500, 6 to 1500, 2.5 to 1000, 3 to 1000, 4 to 1000, 5 to 1000, 6 to 1000, 2.5 to 500, 3 to 500, 4 to 500, 5 to 500, 6 to 500, 2.5 to 100, 3 to 100, 4 to 100, 5 to 100, or 6 to 100. In the embodiments of the present specification, the HOCMM having a defined long-range mesoporous order generated by the method described in the present specification has a total pore volume of about 0.01 to 1.50, 0.01 to 1.0, 0.01 to 0.75, 0.01 to 0.65, 0.1 to 1.50, 0.1 to 1.0, 0.1 to 0.75, 0.1 to 0.65, 0.2 to 1.50, 0.2 to 1.0, 0.2 to 0.75, 0.2 to 0.65, 0.3 to 1.50, 0.3 to 1.0, 0.3 to 0.75, or 0.3 to 0.65 cc / g.

[0065] In the embodiments of this specification, the products generated and demonstrated by the above method in the examples of this specification are characterized by a mesophase having cubic symmetry. In certain embodiments, the product is a 3D-cubic ordered mesoporous zeolite. The HOCMM having a mesophase with cubic symmetry is characterized by the cubic mesoporous channel direction having CMM micropore channels within the walls of the mesostructure. The cubic mesophase can possess one of the symmetries of Ia-3d, Fm-3m, Pm-3n, Pn-3m, or Im-3m. In the embodiments of this specification, the cubic mesophase possesses Ia-3d symmetry, and the secondary XRD peaks associated with the periodic arrangement configuration of the mesopores are present in one or more of the (220), (321), (400), (420), and (332) reflections. In the embodiments of this specification, the cubic mesophase possesses Ia-3d symmetry, and the high degree of long-range cubic mesophase order is observable by microscopy as seen by an electron beam directed along an appropriate zone axis, such as the

[0311] ,

[0111] , or

[0110] zone axis. In the embodiments of this specification, nitrate (NO3 -) is used when an ionic co-solute is used to generate a mesophase having cubic symmetry. In these embodiments, the CMM structure is arranged in cubic symmetry on the mesoscale, and the CMM particles (regardless of their atomic-level symmetry or structure) are arranged around the micelles (on the mesoscale), thereby arranging micelles exhibiting cubic symmetry. Thus, a HOCMM having a cubic mesophase is a CMM characterized by atomic-level symmetry and possessing micropores specific to that type of CMM, arranged in cubic symmetry at the mesoscale level together with mesopores, and the walls of the mesopores and a group of mesostructures between the mesopores are characterized by the said CMM (e.g., crystalline zeolite). This is created as described herein by forming oligomers of the underlying CMM and arranging those oligomers around micelles exhibiting cubic symmetry on the mesoscale. In one embodiment, a HOCMM is provided that includes an NFI zeolite having orthorhombic symmetry at the atomic level arranged in cubic-symmetric mesoscale, where oligomers of the parent MFI zeolite are formed during the synthesis of hierarchical zeolites from the parent MFI zeolite and are arranged around micelles exhibiting cubic symmetry on the mesoscale. In one embodiment, a HOCMM is provided that includes a CHA zeolite having trigonal symmetry at the atomic level arranged in cubic-symmetric mesoscale, where oligomers of the parent CHA zeolite are formed during the synthesis of hierarchical zeolites from the parent CHA zeolite and are arranged around micelles exhibiting cubic symmetry on the mesoscale. In one embodiment, a HOCMM is provided that includes a BEA zeolite having tetragonal symmetry at the atomic level arranged in cubic-symmetric mesoscale, where oligomers of the parent BEA zeolite are formed during the synthesis of hierarchical zeolites from the parent BEA zeolite and are arranged around micelles exhibiting cubic symmetry on the mesoscale. In one embodiment, a HOCMM is provided that includes a MWW zeolite having hexagonal symmetry at the atomic level arranged in cubic-symmetric mesoscale, where oligomers of the parent MWW zeolite are formed during the synthesis of hierarchical zeolites from the parent MWW zeolite and are arranged around micelles exhibiting cubic symmetry on the mesoscale.In one embodiment, an HOCMM is provided that includes an FAU zeolite having atomic-level cubic symmetry arranged and configured at the cubic symmetry mesoscale. During the synthesis of the hierarchical ordered zeolite from the parent FAU zeolite, oligomers of the parent FAU zeolite are formed and arranged around micelles that exhibit cubic symmetry at the mesoscale.

[0066] In the embodiments of this specification, the products generated by the above method and demonstrated in the examples of this specification are characterized by a mesophase having hexagonal symmetry. In certain embodiments, the product is a 2D-hexagonal crystalline ordered mesoporous zeolite. The HOCMM with a mesophase having hexagonal symmetry is characterized by the direction of the hexagonal mesoporous channels with CMM micropore channels in the walls of the mesostructure. The hexagonal mesophase can possess one of p6m, p6mm, or p63 / mmc symmetry. In the embodiments of this specification, the hexagonal mesophase possesses p6mm symmetry, and the secondary XRD peaks related to the periodic arrangement configuration of the mesopores are present in one or more of the (11) and (20) reflections. In the embodiments of this specification, the hexagonal mesophase possesses p6mm symmetry, and the secondary XRD peaks are present in both the (11) and (20) reflections. In the embodiments of this specification, the hexagonal mesophase possesses p6mm symmetry, and the advanced long-range hexagonal p6mm mesophase order is observable by microscopy looking at electron beams perpendicular to the pores along the

[0110] zone axis and / or parallel to the pores along the

[0001] zone axis. In these embodiments, the CMM structure is arranged in a hexagonal p6mm symmetry at the mesoscale, and the CMM particles (regardless of their atomic-level symmetry or structure) are arranged around the micelles (at the mesoscale), thereby arranging micelles exhibiting hexagonal symmetry. Thus, the HOCMM having a hexagonal p6mm mesophase includes CMMs characterized by atomic-level symmetry and possesses micropores specific to that type of CMM, which are arranged in a hexagonal p6mm symmetry at the mesoscale level together with the mesopores, and the walls of the mesopores and a group of mesostructures between the mesopores are characterized by the said CMM (e.g., crystalline zeolite). This is created as described herein by forming oligomers of the underlying CMM and arranging those oligomers around micelles exhibiting hexagonal symmetry at the mesoscale.In one embodiment, an HOCMM is provided that includes an MFI zeolite having atomic-level rhombic symmetry arranged and configured on a hexagonal p6mm symmetry mesoscale. During the synthesis of the hierarchical ordered zeolite from the parent MFI zeolite, the oligomers of the parent MFI zeolite are formed and arranged around micelles that exhibit hexagonal symmetry on the mesoscale. In one embodiment, an HOCMM is provided that includes a CHA zeolite having atomic-level trigonal symmetry arranged and configured on a hexagonal p6mm symmetry mesoscale. During the synthesis of the hierarchical ordered zeolite from the parent CHA zeolite, the oligomers of the parent CHA zeolite are formed and arranged around micelles that exhibit hexagonal symmetry on the mesoscale. In one embodiment, an HOCMM is provided that includes a BEA zeolite having atomic-level tetragonal symmetry arranged and configured on a hexagonal p6mm symmetry mesoscale. During the synthesis of the hierarchical ordered zeolite from the parent BEA zeolite, the oligomers of the parent BEA zeolite are formed and arranged around micelles that exhibit hexagonal symmetry on the mesoscale. In one embodiment, an HOCMM is provided that includes an MWW zeolite having atomic-level hexagonal symmetry arranged and configured on a hexagonal p6mm symmetry mesoscale. During the synthesis of the hierarchical ordered zeolite from the parent MWW zeolite, the oligomers of the parent MWW zeolite are formed and arranged around micelles that exhibit hexagonal symmetry on the mesoscale. In one embodiment, an HOCMM is provided that includes an FAU zeolite having atomic-level cubic symmetry arranged and configured on a hexagonal p6mm symmetry mesoscale. During the synthesis of the hierarchical ordered zeolite from the parent FAU zeolite, the oligomers of the parent FAU zeolite are formed and arranged around micelles that exhibit hexagonal symmetry on the mesoscale.

[0067] In the embodiments of this specification, the products generated by the above method and demonstrated in the examples of this specification are characterized by a high degree of long-range lamellar mesophase order. In certain embodiments, the product is a lamellar mesoporous zeolite with a lamellar mesophase order. The HOCMM with a mesophase having lamellar symmetry is characterized by the lamellar mesoporous channel direction with CMM micropores in the walls of the mesostructure. In these embodiments, the CMM structure is arranged and configured with lamellar symmetry at the mesoscale, and the CMM particles (regardless of their atomic-level symmetry or structure) are arranged and configured around the micelles (at the mesoscale), whereby the micelles are arranged and configured such that those exhibiting lamellar symmetry are present. In certain embodiments, the lamellar symmetry is p2, p1, or pm symmetry. In certain embodiments, the lamellar symmetry is p2 symmetry with secondary XRD peaks associated with the periodic arrangement of mesopores present in at least the (200) reflection. In certain embodiments, the high degree of long-range lamellar mesophase order is observable by microscopy looking at electron beams parallel or perpendicular to the

[0100] zone axis. Thus, the HOCMM having a lamellar mesophase contains CMMs characterized by atomic-level symmetry and possesses micropores inherent to that type of CMM, which together with the mesopores are arranged and configured with lamellar symmetry at the mesoscale level, and the walls of the mesopores and a group of mesostructures between the mesopores are characterized by the said CMM. This is created as described herein by forming oligomers of the underlying CMM and arranging and configuring those oligomers around micelles exhibiting lamellar symmetry at the mesoscale. In one embodiment, an HOCMM is provided that includes an MFI zeolite having atomic-level orthorhombic symmetry arranged and configured with lamellar symmetry at the mesoscale, and during the synthesis of the hierarchical ordered zeolite from the parent MFI zeolite, the oligomers of the parent MFI zeolite are formed and arranged around micelles exhibiting lamellar symmetry at the mesoscale. In one embodiment, an HOCMM is provided that includes a CHA zeolite having atomic-level trigonal symmetry arranged and configured with lamellar symmetry at the mesoscale, and during the synthesis of the hierarchical ordered zeolite from the parent CHA zeolite, the oligomers of the parent CHA zeolite are formed and arranged around micelles exhibiting lamellar symmetry at the mesoscale.In one embodiment, an HOCMM is provided that includes a BEA zeolite having atomic-level square symmetry arranged and configured at the lamellar symmetry mesoscale. During the synthesis of the hierarchical ordered zeolite from the parent BEA zeolite, the oligomers of the parent BEA zeolite are formed and arranged around micelles that exhibit lamellar symmetry at the mesoscale. In one embodiment, an HOCMM is provided that includes an MWW zeolite having atomic-level hexagonal symmetry arranged and configured at the lamellar symmetry mesoscale. During the synthesis of the hierarchical ordered zeolite from the parent MWW zeolite, the oligomers of the parent MWW zeolite are formed and arranged around micelles that exhibit lamellar symmetry at the mesoscale. In one embodiment, an HOCMM is provided that includes an FAU zeolite having atomic-level cubic symmetry arranged and configured at the lamellar symmetry mesoscale. During the synthesis of the hierarchical ordered zeolite from the parent FAU zeolite, the oligomers of the parent FAU zeolite are formed and arranged around micelles that exhibit lamellar symmetry at the mesoscale.

[0068] In embodiments where the CMM structure is arranged in lamellar symmetry at the mesoscale, the lamellar symmetry is mainly observed in the as-made material (i.e., before calcination). In the absence of CMM interconnectivity between the lamellar structures, there is a tendency to collapse during calcination. In certain embodiments, CMMs such as the zeolitic crystalline structures arranged in lamellar symmetry provided herein can exfoliate to form sheet-like CMMs, such as zeolite nanosheets. In certain embodiments, CMMs such as the zeolitic crystalline structures arranged in lamellar symmetry provided herein can retain the lamellar symmetry by using columnarization techniques known in the art. For example, silica sources such as tetraethyl orthosilicate (TEOS) condense within the lamellar structure and crystallize during calcination to retain the lamellar structure and prevent collapse (see, e.g., Na, K., et al., “Pillared MFI Zeolite Nanosheets of a Single-unit-cell Thickness.” J. Am. Chem. Soc. 132, 4169 - 4177). In embodiments where the HOCMMs formed herein possess a lamellar symmetry with a mesoscale columnarized lamellar structure, they can be used, for example, as catalyst materials or catalyst support materials.

[0069] The HOCMMs produced according to the present disclosure are effective as catalysts or catalyst components in the hydrocracking of hydrocarbon oils. The HOCMMs can be used as a support on which one or more active persistent components are loaded on the surface as a hydrocracking catalyst. The active metal component is loaded on a surface including the mesopore wall surface, the micropore wall surface, or the mesopore and micropore wall surfaces, and is, for example, retained; the active metal component is loaded according to known methods such as providing an aqueous solution of the active metal component and subjecting the HOCMM as a catalyst support material to immersion, incipient wetness, and evaporation, or any other suitable method. In certain embodiments, the CMMs of the HOCMMs contain zeolite. In certain embodiments, the CMMs of the HOCMMs are one or more zeolite-type AEIs. *It includes BEA, CHA, FAU, MFI, MOR, LTL, LTA, or MWW. In certain embodiments, the CMM of the HOCMM includes a FAU zeolite.

[0070] The contents of the HOCMM and the active metal component are appropriately determined according to the target. In certain embodiments, the hydrocracking catalyst includes the HOCMM as a carrier and typically includes an inorganic oxide component as a binder and / or a granulating agent. For example, the carrier particles (before loading one or more hydrocracking active metal components) can contain the HOCMM in the range of about 0.1 - 99, 0.1 - 90, 0.1 - 80, 0.1 - 70, 0.1 - 50, 0.1 - 40, 2 - 99, 2 - 90, 2 - 80, 2 - 70, 2 - 50, 2 - 40, 20 - 100, 20 - 90, 20 - 80, 20 - 70, 20 - 50, or 20 - 40% by mass, and the remaining content is an inorganic oxide. In certain embodiments, the carrier particles (before loading one or more hydrocracking active metal components) can contain the HOCMM in the range of about 0.1 - 99, 0.1 - 90, 0.1 - 80, 0.1 - 70, 0.1 - 50, 0.1 - 40, 2 - 99, 2 - 90, 2 - 80, 2 - 70, 2 - 50, 2 - 40, 20 - 100, 20 - 90, 20 - 80, 20 - 70, 20 - 50, or 20 - 40% by mass, and the remaining content is an inorganic oxide and one or more other zeolite-based materials.

[0071] As the inorganic oxide component, any material used in hydrocracking or other catalyst compositions in related technologies can be used. Examples thereof include alumina, silica, titania, silica - alumina, alumina - titania, alumina - zirconia, alumina - boria, phosphorus - alumina, silica - alumina - boria, phosphorus - alumina - boria, phosphorus - alumina - silica, silica - alumina - titania, silica - alumina - zirconia, alumina - zirconia - titania, phosphorus - alumina - zirconia, alumina - zirconia - titania, and phosphorus - alumina - titania.

[0072] The active metal component can include one or more metals or metal compounds (oxides or sulfides) known in the field of hydrocracking, including those selected from Groups 6, 7, 8, 9, and 10 of the IUPAC Periodic Table. In certain embodiments, the active metal component is one or more of Mo, W, Co, or Ni (oxides or sulfides). Additional active metal components can be contained in the catalyst at effective concentrations. For example, the total active component content in the hydrocracking catalyst can be present in amounts known in the relevant art, e.g., about 0.01 - 40, 0.1 - 40, 1 - 40, 2 - 40, 5 - 40, 0.01 - 30, 0.1 - 30, 1 - 30, 2 - 30, 5 - 30, 0.01 - 20, 0.1 - 20, 1 - 20, 2 - 20, or 5 - 20 wt% with respect to the metal, oxide, or sulfide. In certain embodiments, the active metal component is loaded using a solution of the oxide and, prior to use, the hydrocracking catalyst is sulfided.

Examples

[0073] The HOCMMs produced in the examples herein exhibit a significant degree of defined long-range mesoporous order, as given by the low-angle XRD patterns. The structural and textural properties of certain samples are presented in Table 3. The parent zeolites used in the examples and comparative examples possess the FAU framework and zeolite Y (obtained from Zeolyst International, product name CBV 720), which is referred to herein as zeolite HY-15 and has an SAR of about 30 (Si / Al atomic ratio of 15). The examples are shown with respect to this particular zeolite, but the methods herein can be applied to other parent CMMs obtained from different synthetic processes or commercial manufacturers and from other sources and of other types described herein. Thus, the resulting compositions have a mesoporous structure with microporosity and a CMM structure corresponding to the parent CMM. The solutions were prepared at room temperature (RT) with stirring at 500 RPM.

[0074] Characterization in this specification was carried out as follows. The powder X-ray diffraction pattern was obtained using a Bruker D8 dual diffractometer operating at 40 kV and 40 mA with Cu Kα radiation (λ = 0.154 nm) and a step size of 0.02. N2 physisorption measurements were performed at 77 K using a Micrometrics ASAP 2420 instrument. All samples were degassed at 350 °C for 12 hours prior to analysis. The specific surface area and pore size distribution were calculated using the Brunauer-Emmett-Teller (BET) and non-local density functional theory (NLDFT) models. The micropore volume was calculated using the t-plot method. High-resolution transmission electron microscopy (TEM) studies were conducted using an FEI-Titan ST electron microscope operating at 300 kV. Scanning electron microscopy (SEM) images were obtained using a Nova Nano HR-SEM 240 microscope operating at 4 kV. The samples were sputter-coated with platinum (Pt) prior to analysis to eliminate the charging effect. The Si / Al ratio was calculated by solid-state magic angle spinning nuclear magnetic resonance (MAS-NMR) experiments using a Bruker Advance 400 MHz instrument applying a 4 μs high-frequency pulse and a 60 s recycle delay. Conversely, the bulk Si / Al ratio of the zeolite was calculated from an analysis performed by inductively coupled plasma-optical emission spectroscopy (ICP-OES) using a 5100 ICP-OES Agilent instrument. Prior to analysis, the samples were mixed with hydrofluoric acid (HF) and nitric acid (HNO3) and decomposed at 260 °C and 160 bar using an Ultra WAVE microwave digestion system (Milestone).

[0075] For obtaining electron micrographs for tomography reconstruction, zeolite powder was deposited on a Quantifoil 300 mesh TEM grid supporting a continuous carbon film with a thickness of 2 nm on a perforated carbon film. Before zeolite deposition, a dilute solution of gold nanoparticles (AuNP) with a diameter of about 5 nm was dispersed on the TEM grid. The AuNP will be used for alignment of serial tilt images of the tomography. To protect the specimen from radiation-induced damage during the long exposure time required for tomography data acquisition, the acquisition of serial tilt images of the tomography was performed on a Krios G4 (ThemoFisher (trademark)) electron microscope at liquid nitrogen temperature. The actual temperature at the stage level was about 183 °C. Serial tilt images were acquired in energy filter (EF) mode using a 30 eV slit to increase the contrast of bright-field TEM images. Detection was performed with a Falcon i electron direct detector camera operating in electron counting mode with a 4096 pixel frame size. To keep the total exposure dose low, only sample tracking was performed after each serial tilt image during data acquisition. Refocusing was performed manually about every 10 images. The angular range was ±64°, and the tilt step was 1°. Serial tilt images were aligned with IMOD software using 13 AuNP as fiducial markers that were clearly visible at each tilt. Before reconstruction, image binning 2 was performed to increase the SNR and reduce the calculation time. To enhance the visibility of pores in the 3D tomogram, the images were filtered using an average background subtraction filter (ABSF) implemented as a script in Digital Micrograph. The SIRT reconstruction algorithm was executed with 100 iterations using a relaxation factor of 1.

[0076] (Example 1A) An amount of 2.4 grams of NH4OH was added to 28.3 grams of water while stirring. An amount of 1.0 gram of dry zeolite HY-15 was dispersed in this solution and stirred for an additional 0.25 hour. Then, an amount of 0.4 gram of CTAB was added and stirred for an additional 0.5 hour. The resulting solution was stirred for an additional 1 hour and then subjected to hydrothermal treatment at 130 °C for 24 hours. The resulting solid was filtered, washed with water, and dried at 120 °C for 24 hours. The synthesized product was calcined in air at 550 °C for 6.0 hours at a heating rate of 60 °C / hour to obtain AH-T (where AH refers to ammonium hydroxide and CT refers to CTAB). The AH-CT synthesized according to this procedure exhibited disordered mesoporosity, was characterized in FIGS. 3A - 4B, the SEM image is presented in FIG. 6, and the structural and textural properties are presented in Table 3.

[0077] In an alternative procedure, an amount of 2.0 grams of dry zeolite HY-15 was dispersed in 56.6 grams of water while stirring. An amount of 0.77 gram of cetyltrimethylammonium bromide (CTAB) was added to this solution and stirred for an additional 0.5 hour. Then, 4.75 grams of aqueous ammonium hydroxide (30 mass%) was added dropwise to the stirred mixture. The resulting solution was stirred for an additional 0.5 hour and then subjected to hydrothermal treatment at 130 °C for 24 hours. The resulting solid was filtered, washed with water, and dried at 120 °C for 24 hours. The synthesized product was calcined in air at 550 °C for 6.0 hours at a heating rate of 60 °C / hour to obtain AH-CT exhibiting disordered mesoporosity.

[0078] (Example 1B) A procedure for synthesizing 2D - hexagonal ordered mesoporous FAU - type zeolite is provided. An amount of 2.4 grams of NH4OH was added to 28.3 grams of water while stirring. An amount of 1.0 gram of dry zeolite HY - 15 was dispersed in the base solution and stirred for an additional 0.25 hour. Then, an amount of 1.5 milliliters of dimethyloctadecyl(3 - trimethoxysilyl - propyl) - ammonium chloride (DOAC) (42.0 mass% in methanol) was added and stirred for an additional 0.5 hour. The resulting solution was stirred for an additional 1 hour and then hydrothermally treated at 130 °C for 24 hours. The resulting solid was filtered, washed with water, and dried at 120 °C for 24 hours. The synthesized product was calcined in air at 550 °C for 6.0 hours at a heating rate of 60 °C / hour to obtain AH - TMS (where TMS refers to DOAC, dimethyloctadecyl(3 - trimethoxysilyl - propyl) - ammonium chloride). The AH - TMS formed by this procedure exhibits 2D - hexagonal ordered mesoporous symmetry, is characterized in FIGS. 3A - 4B, the SEM image is presented in FIG. 6, and the structural and textural properties are presented in Table 3.

[0079] In an alternative procedure, an amount of 2.0 grams of dry zeolite HY - 15 was dispersed in 56.6 grams of water while stirring. To this dispersion, an amount of 3.0 milliliters of the organic silane, DOAC (42.0 mass% in methanol), was added and stirred for an additional 0.5 hour. Then, 4.75 grams of an aqueous ammonium hydroxide solution (30 mass%) was added dropwise to the stirred mixture. The resulting solution was stirred for an additional 0.5 hour and then hydrothermally treated at 130 °C for 24 hours. The resulting solid was filtered, washed with water, and dried at 120 °C for 24 hours. The synthesized product was calcined in air at 550 °C for 6 hours at a heating rate of 60 °C / hour to obtain AH - TMS. The AH - TMS formed by this procedure possesses 2D - hexagonal ordered mesoporous symmetry (as evident in the TEM images of this AH - TMS presented in FIGS. 5A - 5C).

[0080] (Example 1C) An amount of 0.6 grams of urea was added to 28.3 grams of water to form a homogeneous solution. To this solution, an amount of 1.0 gram of dry zeolite HY-15 was dispersed and stirred for an additional 0.5 hour. Thereafter, 20 milliliters of water and 1.5 milliliters of DOAC (42.0 mass% in methanol) were added and stirred for an additional 2 hours. The resulting solution was subjected to hydrothermal treatment at 130 °C for 5 days. The resulting solid was filtered, washed with water, and dried at 120 °C for 24 hours. The synthesized product was calcined in air at 550 °C for 6.0 hours at a heating rate of 60 °C / hour to obtain U-TMS (where U refers to urea). The U-TMS formed by this procedure exhibited poorly defined mesoporosity, was characterized in FIGS. 3A - 4B, the SEM images are presented in FIG. 6, and the structural and textural properties are provided in Table 3.

[0081] In an alternative procedure, an amount of 1.2 grams of urea was dissolved in 60.0 grams of water to form a homogeneous solution. To this mixture, 2.0 grams of dry zeolite HY-15 were added and stirred for 10 minutes. Thereafter, 3.0 milliliters of DOAC (42.0 mass% in methanol) were added. The resulting solution was stirred for 0.5 hour and then subjected to hydrothermal treatment at 130 °C for 72 hours. The resulting mixture was filtered, washed with water, and dried at 120 °C for 24 hours. The synthesized product was calcined in air at 550 °C for 6 hours at a heating rate of 60 °C / hour to obtain U-TMS that did not possess well-defined mesoporosity.

[0082] The calcined products from Examples 1A - 1C and the reference HY-15 zeolite were characterized in FIGS. 3A - 4B: FIG. 3A shows a low-angle XRD pattern, FIG. 3B shows a high-angle XRD pattern, the intensity of which is represented in arbitrary units (a.u.) plotted against the frequency 2θ (°); FIG. 4A shows a N2 physical adsorption isotherm plotting adsorbed N2 (cm 3 ·g -1 ) against the relative pressure (P / P0); and FIG. 4B shows dV / dlogW (cm 3 ·g -1) is plotted, showing the non-localized density functional theory (NLDFT) pore size distribution (where "a" corresponds to commercial USY (zeolite HY-15), "b" corresponds to AH-CT, "c" corresponds to AH-TMS, and "d" corresponds to U-TMS). In Example 1B, the resulting hierarchical zeolite is arranged to be hexagonal as observed in the

[0100] and

[0110] directions, and is a 2D-hexagonal ordered mesoporous FAU-type zeolite having mesoporous channels with FAU micropore channels in the walls and a group of mesostructures between the mesopores.

[0083] Figures 5A - 5C are TEM micrographs of calcined AH-TMS (formed by an alternative procedure of Example 1B) showing hexagonal mesoporous channels in the

[0100] and

[0110] directions: Figure 5A shows the TEM micrograph at a scale of 50 nanometers; Figure 5B shows the TEM micrograph in the

[0100] direction and the

[0110] direction at a scale of 20 nanometers, and also shows the corresponding schematic diagram and unit cell dimensions; and Figure 5C shows the TEM micrograph in the

[0100] direction at a scale of 10 nanometers (with an overlapping schematic diagram of the underlying zeolite structure).

[0084] Figure 6 shows SEM images of (A) the parent zeolite, HY-15, and the calcined product of the present specification, (B) AH-CT, (C) AH-TMS, and (D) U-TMS. The image (B) for AH-CT shows no significant change in morphology even at the edges of the crystals, whereas the image of AH-TMS shows a change in morphology suggesting the functionality of the organosilane, having a bulkier head group and silanol groups than CTAB, and resulting in improved decomposition and reassembly. For U-TMS, the urea-mediated synthesis significantly improves the crystallinity (image (D) in Figure 6), however the mesoporous structure is poorly defined as evident from the pattern (d) in Figure 3A. Without being bound by theory, these contrasting results suggest that the decomposition rate affects not only recrystallization but also supramolecular self-assembly. The organization of the mesophase can be affected by numerous physicochemical phenomena including Coulombic interactions, hydration energy, and hydrophobic effects between organic and inorganic species. In the absence of strong alkali cations, surfactant-zeolite interactions play an important role in promoting cooperative self-assembly to induce the mesophase. In the case of AH-TMS, the decomposition of the zeolite is instantaneous, and importantly, the -Si(OCH3)3 groups on the organosilane head groups can readily hydrolyze and interact with the anionic zeolite component, resulting in the promotion of the mesophase. Conversely, in the case of U-TMS, the concentration of the anionic inorganic component changes gradually over time, thus the charge balance at the micelle interface changes progressively and the mesophase formation collapses.

[0085] The high long-range order is evident from the low-angle XRD pattern “c” of Figure 3A showing Bragg reflections at angles corresponding to the 100, 110, and 200 planes, which suggest hexagonal mesopore symmetry in AH-TMS. Conversely, in Example 1A, the use of a relatively small template or surfactant molecule (CTAB) causes diffusion within the zeolite pores, leading to heterogeneous decomposition and preventing comprehensive reorganization. This is evident from the angular XRD patterns “b” and “d” that did not show high long-range order despite having a uniform pore size distribution (PSD) from the corresponding N2 physical adsorption isotherm (Figure 4A), due to heterogeneous zeolite decomposition and limited supramolecular self-assembly. The retention of the underlying zeolite structure is evident from the high-angle XRD patterns of Figure 3B for all samples, without conflicting with the case of the parent zeolite, FAU zeolite. Furthermore, AH-TMS demonstrates excellent hierarchical ordered mesoporosity, as shown by the characteristic type-IV isotherm with H1 hysteresis (Figure 4A). Additionally, the high mesopore volume and narrow pore size distribution further support the existence of long-range ordered mesoporosity (Figure 4B).

[0086] (Example 2A) A procedure for synthesizing 3D-cubic ordered mesoporous FAU-type zeolite is provided. An amount of 0.6 grams of urea was added to 10.0 grams of water to form a homogeneous solution. To this solution, an amount of 1.0 gram of dry zeolite HY-15 was added and stirred for 0.5 hour. Thereafter, 20 milliliters of water, 0.1 gram of ammonium nitrate (NH4NO3) as a source of ionic co-solute, and 1.5 milliliters of DOAC (42.0 mass% in methanol) were added stepwise, and the mixture was stirred for a further 2 hours. The resulting solution was subjected to hydrothermal treatment at 130 °C for 5 days. The resulting solid was filtered, washed with water, and dried at 120 °C for 24 hours. The synthesized product was calcined in air at 550 °C for 6.0 hours at a heating rate of 60 °C / hour to obtain U-N-TMS-130 (where N refers to nitrate and "130" refers to the hydrothermal treatment temperature). The U-N-TMS-130 formed by this procedure exhibits 3D-cubic ordered mesoporous symmetry, is characterized in FIGS. 7A to 8B, TEMs are presented in FIGS. 9A to 9C and the structural and textural properties are presented in Table 3.

[0087] In an alternative procedure, an amount of 1.2 grams of urea was dissolved in 60.0 grams of water to form a homogeneous solution. To this mixture, 0.2 gram of ammonium nitrate (NH4NO3) as a source of ionic co-solute was added and stirred to form a homogeneous solution. 2.0 grams of zeolite HY-15 were added and stirred for 10 minutes. Thereafter, 30 milliliters of DOAC (42.0 mass% in methanol) were added. The resulting solution was stirred for 0.5 hour and then subjected to hydrothermal treatment at 130 °C for 72 hours. The resulting solid was filtered, washed with water, and dried at 120 °C for 24 hours. The synthesized product was calcined in air at 550 °C for 6 hours at a heating rate of 60 °C / hour to obtain U-N-TMS. The calcined U-N-TMS formed by this procedure exhibits 3D-cubic ordered mesoporous symmetry as is evident from the TEM images presented in FIGS. 10A to 10B.

[0088] (Example 2B) Using 1.0 gram of urea and 2.0 milliliters of DOAC (42.0 mass% in methanol), and following a procedure similar to that disclosed herein in the first procedure of Example 2A, except that the hydrothermal treatment was carried out at 150 °C for 72 hours. The calcined product is U-N-TMS-150 having 3D-cubic ordered mesoporous symmetry. U-N-TMS-150 from this procedure is characterized in FIGS. 7A - 8B, its TEM images are presented in FIGS. 12A - 12C, and the structural and textural properties are presented in Table 3.

[0089] The calcined mesoporous zeolite products from Examples 2A and 2B and the reference HY-15 zeolite are characterized in FIGS. 7A - 8B: FIG. 7A shows a low-angle XRD pattern, FIG. 7B shows a high-angle XRD pattern, the intensity of which is represented in arbitrary units (a.u.) plotted against the frequency 2θ (°); FIG. 8A shows a N2 physical adsorption isotherm plotting adsorbed N2 (cm 3 ·g -1 ) against the relative pressure (P / P0); and FIG. 8B shows a non-local density functional theory (NLDFT) pore size distribution plotting dV / dlogW (cm 3 ·g -1 ), where "a" corresponds to commercial-USY (zeolite HY-15), "b" corresponds to U-N-TMS-130, and "c" corresponds to U-N-TMS-150. In Examples 2A and 2B, the hierarchical ordered zeolite of the product is a 3D-cubic ordered mesoporous FAU-type zeolite having cubic mesoporous channels in the

[0100] and

[0110] directions, with FAU micropore channels in the walls of the mesopores and a group of mesostructures between the mesopores.

[0090] Figures 9A - 9C present TEM micrographs of calcined U - N - TMS - 130 formed by the first procedure of Example 2A, showing cubic mesoporous channels in the

[0111] and

[0110] directions. Figure 9A is an image in the

[0111] direction at a scale of 100 nanometers, and Figures 9B and 9C are images in the

[0112] direction at a scale of 50 nanometers (the image in Figure 9B is magnified relative to the image in Figure 9C). Figures 10A - 10B are TEM micrographs of calcined U - N - TMS formed by the second procedure of Example 2A, showing cubic mesoporous channels in the

[0111] and

[0110] directions: Figure 10A shows the TEM micrograph at a scale of 100 nanometers; Figure 10B shows TEM photographs in the

[0110] direction and the

[0111] direction at a scale of 20 nanometers; and Figure 10C shows a schematic of the FAU unit cell and dimensions and an arrangement configuration providing their long - range mesoporous order. The high degree of long - range order is evident from the low - angle XRD pattern of Figure 7A, which is characteristic of a bicontinuous gyroid (cubic) (Ia - 3d) mesopore symmetry (reflections at 321, 400, 420, and 332 are broadened), showing Bragg reflections 211, 220, 321, 400, 420, and 332. The retention of the underlying zeolite structure is evident from the high - angle XRD pattern of Figure 7B, which is consistent with that of the parent zeolite, FAU zeolite. Furthermore, U - N - TMS - 130 and U - N - TMS - 150 demonstrate excellent hierarchical - ordered mesoporosity, as shown by the characteristic type - IV isotherm with H1 hysteresis shown in the N2 physisorption isotherm of Figure 8A. Additionally, the high mesopore volume and narrow pore size distribution demonstrated in Figure 8B further support the existence of long - range - ordered mesoporosity. Figure 11 represents the electron tomography reconstruction of U - N - TMS - 150, and its inset shows an enlarged pore architecture and an overlay of the structure.Figures 12A - 12C present TEM micrographs of U - N - TMS - 150 along with corresponding structural diagrams. Figure 12A is an image showing the TEM micrograph at a scale of 20 nanometers with a

[0100] orientation, Figure 12B is an image at a scale of 50 nanometers with a

[0110] orientation, and Figure 12C is an image at a scale of 10 nanometers with a

[0111] orientation. The inset in Figures 12A and 12B shows an enlarged image, and the inset in Figure 12C shows selected area electron diffraction (SAED). U - N - TMS - 150 synthesized at higher temperatures demonstrated improved textural properties as a result of the complete removal of non - framework aluminum. The 3D mesostructure by electron tomography (ET) revealed a homogeneous distribution of mesoporous channels within the zeolite volume. A longitudinal slice cut through the center of the zeolite grain shows a continuous network of mesopores formed along the crystallographic direction. The inset in Figure 11 emphasizes the 3D spatial homogeneity of the hierarchical pore architecture. The interconnected mesopore network formed by the zeolite framework extends from the outer surface to the core of the zeolite grain.

[0091] Furthermore, when the product of the IC of the example (U - TMS) was compared with the products of Examples 2A and 2B (U - N - TMS), the benefit of the ionic cosolute involvement of nitrate was evident. The ionic cosolute acts to influence the cubic micelle shape by the Hofmeister effect, around which FAU - type zeolite oligomers are arranged. In Example 1C, there is some periodicity in the mesopore arrangement, perhaps from either a bimodal or structural collapse, however, there is a marked lack of any long - range order compared to the products of Examples 2A and 2B having nitrate anions, as observed by low - angle XRD showing the reflection characteristics of the gyro - dial co - continuous (cubic) mesopore structure (Ia - 3d).

[0092] (Example 3A) A procedure for synthesizing 2D-hexagonal ordered mesoporous FAU-type zeolite using sulfate as an ionic co-solute is provided. An amount of 0.6 grams of urea was added to 10.0 grams of water to form a homogeneous solution. To this solution, an amount of 1.0 gram of dry zeolite HY-15 was added and stirred for 0.5 hour. Then, 20 milliliters of water, 0.165 grams of ammonium sulfate ((NH4)2SO4), and 1.5 milliliters of DOAC (42.0 mass% in methanol) were added stepwise, and the mixture was stirred for an additional 2 hours. The resulting solution was subjected to hydrothermal treatment at 130 °C for 72 hours. The obtained solid was filtered, washed with water, and dried at 120 °C for 24 hours. The synthesized product was calcined in air at 550 °C for 6.0 hours at a heating rate of 60 °C / hour to obtain U-S-TMS (where U refers to urea, S refers to sulfate, and TMS refers to DOAC). The U-S-TMS formed by this procedure exhibits 2D-hexagonal ordered mesoporous symmetry, is characterized in FIGS. 13A to 14B, TEM images are presented in FIGS. 15A to 15E, and the structural and textural properties are presented in Table 3.

[0093] In an alternative procedure, an amount of 1.2 grams of urea was dissolved in 60.0 grams of water to form a homogeneous solution. To this mixture, an amount of 0.33 grams of ammonium sulfate (NH4)2SO4) was added as a source of ionic co-solute and stirred until homogeneous. Then, an amount of 2.0 grams of dry zeolite HY-15 was added and stirred for 10 minutes. Then, 3.0 milliliters of DOAC (42.0 mass% in methanol) was added. The resulting solution was stirred for 0.5 hour and then hydrothermally treated at 130 °C for 72 hours. The obtained solid was filtered, washed with water, and dried at 120 °C for 24 hours. The synthesized product was calcined in air at 550 °C for 6 hours at a heating rate of 60 °C / hour to obtain U-S-TMS having 2D-hexagonal ordered mesoporous symmetry.

[0094] (Example 3B) A procedure for synthesizing 2D-lamellar ordered mesoporous FAU-type zeolite using perchloric acid as an ionic co-solute is provided. An amount of 0.6 grams of urea was added to 10.0 grams of water to form a homogeneous solution. To this solution, an amount of 1.0 gram of dried zeolite HY-15 was added and stirred for 0.5 hour. Then, 20 milliliters of water, 0.46 grams of sodium perchlorate (NaClO4), and 1.5 milliliters of DOAC (60.0 mass% in methanol) were added stepwise, and the mixture was stirred for an additional 2 hours. The resulting solution was subjected to hydrothermal treatment at 130 °C for 72 hours. The resulting solid was filtered, washed with water, and dried at 120 °C for 24 hours. The synthesized product was calcined in air at 550 °C for 6.0 hours at a heating rate of 60 °C / hour to obtain U-C-TMS (where U refers to urea, C refers to perchloric acid, and TMS refers to DOAC). The as-prepared U-C-TMS formed by this procedure exhibits 2D-lamellar ordered symmetry. The as-prepared and calcined U-C-TMS are characterized in Figure 13A. The calcined U-C-TMS is characterized in Figures 13B, 14A - 14B, and the structural and textural properties are presented in Table 3.

[0095] When compared with Examples 3A and 3B, the influence of anion selection is evident. The selection of perchlorate as the ionic co-solute affects the lamellar micelle shape, whereas the selection of nitrate as the ionic co-solute affects the cubic micelle shape due to the Hofmeister effect. In both examples, the FAU-type zeolite oligomers are arranged around the shaped micelles.

[0096] As-prepared and calcined products from Examples 3A - 3B are characterized in Figure 13A, and the calcined products from Examples 3A - 3B are characterized in Figures 13B and 13A - 13B (where "a" corresponds to U - S - TMS and "b" corresponds to U - C - TMS). Figure 13A shows a low - angle XRD pattern, Figure 13B shows a high - angle XRD pattern, the intensity of which is represented in arbitrary units (a.u.) plotted against the frequency 2θ (°), the as - prepared pattern is shown by a dashed line and the calcined pattern is shown by a solid line. Figure 14A shows a N2 physical adsorption isotherm plotting adsorbed N2 (cm 3 ·g -1 ) against the relative pressure (P / P0), and Figure 14B shows a non - localized density functional theory (NLDFT) pore size distribution plotting dV / dlogW (cm 3 ·g -1 ). The high - degree long - range order of as - prepared and calcined U - S - TMS is evident in Figure 13A, where the low - angle XRD pattern shows Bragg reflection peaks 100, 110, and 200, suggesting a 2D - hexagonal ordered mesoporous symmetry. The high - degree long - range order of as - prepared U - C - TMS is also evident in Figure 13A, where Bragg reflection peaks 100 and 200 suggest a 2D - lamellar (p2) mesopore symmetry, but this order is lost when the structure collapses during calcination. The retention of the underlying zeolite structure is evident in Figure 13B, where the high - angle XRD pattern is consistent with that of the parent zeolite, the FAU zeolite.

[0097] Figures 15A - 15E present TEM micrographs of U - S - TMS synthesized in the first procedure of Example 3A. Figure 15A is an image at a scale of 20 nanometers with a corresponding structural diagram, Figure 15B is an enlarged view of a part of the image of Figure 15A with an inset of a fast Fourier transform pattern, Figure 15C is an image at a scale of 50 nanometers showing selected area electron diffraction (SAED) in the inset, Figure 15D is an image at a scale of 50 nanometers, and Figure 15E is an image at a scale of 20 nanometers with a corresponding structural diagram.

[0098] (Example 4A) A procedure for synthesizing 2D-lamellar ordered mesoporous FAU-type zeolite is provided. 1.2 grams of urea was dissolved in 60.0 grams of water to form a homogeneous solution. 2.0 grams of zeolite HY-15 was added to this mixture and stirred. 0.92 grams of sodium perchlorate (NaClO4) was added and stirred for 10 minutes. Then, 3.0 milliliters of DOAC (42.0 mass% in methanol) was added. The resulting solution was stirred for 0.5 hour and then hydrothermally treated at 130 °C for 72 hours. The resulting solid was filtered, washed with water, and dried at 120 °C for 24 hours. The synthesized product was calcined in air at 550 °C for 6 hours at a heating rate of 60 °C / hour to obtain U-C-TMS (Y refers to zeolite Y, C refers to perchlorate, U refers to urea, and TMS refers to DOAC). The as-prepared U-C-TMS formed by this procedure exhibits 2D-lamellar ordered symmetry, is characterized in FIGS. 16A - 16B, and the TEM images are presented in FIGS. 17A - 17C.

[0099] (Example 4B) The procedure follows that of Example 4A except that 4.75 grams of NH4OH is used as the alkali reagent instead of urea.

[0100] In Example 4A, the resulting hierarchical zeolite is a 2D-lamellar ordered mesoporous FAU zeolite having lamellar mesoporous channels with FAU micropore channels in the walls, which exist in the

[0100] direction, and a group of mesostructures between the mesopores. Figure 16A shows a low-angle XRD pattern, Figure 16B shows a high-angle XRD pattern, "a" corresponds to commercial-USY (zeolite HY-15), "b" corresponds to U-C-TMS: Figures 17A to 17C show the U-C-TMS lamellar structure: Figure 17A shows a TEM micrograph at a scale of 50 nanometers with a planar orientation of

[0100] ; Figure 17B shows a TEM micrograph at a scale of 20 nanometers; and Figure 17C shows a TEM micrograph at a scale of 50 nanometers with a planar orientation of

[0110] . The high degree of long-range order is evident from Figure 16A, and the low-angle XRD pattern shows Bragg reflection peaks 100 and 200, suggesting a 2D-lamellar (p2) mesopore symmetry. The retention of the underlying zeolite structure is evident from Figure 16B, and the high-angle XRD pattern is consistent with that of the parent zeolite, the FAU zeolite.

[0101] According to the examples herein, hierarchical ordered FAU frameworks exhibiting 2D-hexagonal (p6mm), 3D-cubic (Ia-3d), and 2D-lamellar (p2) mesopore symmetries are prepared for the first time by systematic post-synthesis reassembly.

[0102] (Example 5) Characterization of acidity: The characterization of acid sites was carried out by Fourier transform infrared spectroscopy (FTIR) using pyridine as a probe molecule and a Nicolet 6700 spectrophotometer. Before analysis, the pelletized sample was degassed at 450 °C under vacuum (10 -5 mbar) for 24 hours. After cooling to room temperature, pyridine vapor was periodically dosed for 0.5 hours. Then, the physically adsorbed pyridine was removed under vacuum at 150 °C for 2 hours, and then the FTIR spectrum was recorded. The quantification of acid sites was carried out using the following formula C BAS = IMEC BAS -1 ×IA BAS ×πR2 / W C LAS = IMEC LAS -1 ×IA LAS ×πR 2 / W is performed using, where C is the concentration (μmol / g zeolite) of acid sites (BAS - Bronsted acid sites, and LAS - Lewis acid sites), and IMEC BAS and IMEC LAS refer to the integrated molar extinction coefficient (BAS - 1.67 cm / μmol; LAS - 2.22 cm / μmol), IA BAS and IA LAS refer to the integrated absorbance (cm -1 ), and R (cm) and W (mg) are the radius and mass of the zeolite pellet / disk.

[0103] Figure 18 shows the FTIR spectra of the parent zeolite (a), and the HOCMM of this specification containing U - N - TMS - 150 (b), and U - S - TMS synthesized in the first procedure of Example 3A. The Bronsted acid sites are indicated at a wavenumber of 1545 cm -1 , and the Lewis acid sites are indicated at a wavenumber of 1445 cm -1 . Table 4 shows the acid properties of the parent zeolite and U - N - TMS - 150 and U - S - TMS synthesized in the first procedure of Example 3A. The overall acidity of the synthesized HOCMM is lower compared to the parent zeolite due to the removal of non - framework - A1 in the parent zeolite during reassembly; the framework A1 is present in the Bronsted acid sites (0.28 mmol / g). The acid sites are reorganized and distributed in the HOCMM as both new Lewis acid sites (about 0.1 mmol / g) and Bronsted acid sites (about 0.25 mmol / g). Despite having a lower concentration of zeolite acid sites compared to the parent zeolite, the synthesized HOCMM is effective as a catalyst support. The ratio of Bronsted / Lewis acid sites is even higher in the case of the synthesized HOCMM compared to the parent zeolite.

[0104] (Example 6) Additional Characterization: Additional properties of the HOCMMs herein, including the parent zeolite (a) and U-N-TMS-150 (b) and U-S-TMS synthesized in the first procedure of Example 3A (c), are shown in FIGS. 19A-19B and 29 determined using Si MAS-NMR and 27 Al MAS-NMR spectroscopy. 29 The Si-NMR spectrum (FIG. 19A) shows two main resonances at about 106 ppm and about 101 ppm, which correspond to silicon atoms in 4Si(0Al) and 3Si(1Al) environments, respectively, and are designated as Q 4 and Q 3' silica. 29 The Si / Al ratio calculated from the Si-NMR spectrum (14.8) and the ratio from inductively coupled plasma analysis (Si / Al about 8.9) reveal that the parent zeolite has nearly 40% of its aluminum as extra-framework species in octahedral coordination, 27 and in the Al-NMR spectrum (FIG. 19B) a sharp resonance (AlO) can be seen at "about 0 ppm". The presence of high extra-framework -Al can be detrimental in catalytic reactions as it causes closure of micropores and changes the selectivity of the product and the composition of coke. In contrast, the HOCMMs characterized herein show a higher concentration of framework -Al atoms in tetrahedral coordination (Al T ) as seen in the broad resonance at "about 60 ppm". In particular, the U-N-TMS-130 pattern (b) shows mostly "Al" atoms in Td coordination. Without being bound by theory, this is expected to be due to thorough dealumination at high synthesis temperatures. Without being bound by theory, the broadness of the Al T resonance related to the HOZ material may be attributed to slight variations in the regenerated periodicity, aluminum distribution, and Al-O bond lengths in the crystal lattice.

[0105] (Example 6) Base-mediated decomposition / cutting: The base-mediated decomposition study of the parent zeolite was carried out at 130 °C in the absence of surfactant to elucidate the nature of the hierarchical order by the post-synthesis ensemble process to promote reorganization at the unit cell level. Figures 20A and 20B show the high-angle XRD patterns of the parent zeolite at various treatment stages. In Figure 20A, the pattern is that of the parent zeolite and after treatment with NH4OH and urea at 130 °C for 1.5 h, and Figure 20B shows the parent zeolite treated with urea at 130 °C after 1.5 h, 6 h, and 18 h. Figure 20C 29 shows the Si MAS-NMR spectrum, and Figure 20D 27 shows the Al MAS-NMR spectrum, which are those of (a) HY-15; (b) after NH4OH treatment at 130 °C / 1.5 h; (c) after urea treatment at 130 °C / 6 h. The high-angle XRD studies (Figures 20A - 20B) reveal that NH4OH decomposes the zeolite into an almost amorphous framework in 1.5 h, while the urea treatment results in partial decomposition even after 6 h. 27 Al- and 29 Si-magic angle spinning-nuclear magnetic resonance (MAS-NMR) spectra (Figures 20C - 20D) suggest that the urea treatment selectively decomposes the Si - O - Si bond without strongly affecting the "Si - O - Al" region, and thus most of the aluminum remains within the tetrahedrally coordinated framework (Al T ~60 ppm). Such a decomposition pattern can result in oligomeric zeolite fragments (Q 4a , Q 3' , Al T ) together with siloxane (Q 4b ) or silanol extension (Q 3 ), which can be easily reorganized into a crystalline mesostructure during heat treatment. The formation of such zeolite fragments (Figure 20E) is a factor in the hierarchical order by the post-synthesis ensemble process for fabricating HOCMM. Without being bound by theory, in the presence of surfactant, the amounts of Q 4b and Q 3 species are predicted to be significantly reduced due to the surfactant - zeolite interaction that limits over-decomposition.

[0106] In the case of base-mediated reassembly, the decomposition of zeolite can result in partially crystalline oligomers, which can recrystallize during hydrothermal (synthesis) and heat treatment (calcination). However, uncontrolled decomposition can lead to isolated amorphous domains and fail to recrystallize due to the absence of appropriate conditions (high alkalinity and inorganic cations). Thus, high concentrations of strong bases such as NaOH and NH4OH can cause uncontrolled decomposition, form amorphous components that cause pore closure, and result in a concentration gradient across the zeolite crystal. Low base concentrations can lead to insufficient zeolite decomposition due to the decrease in base concentration over time. As a result, strategically controlling zeolite decomposition is a factor enabling reassembly into a crystalline mesostructure in the synthesis process described herein for HOCMM.

[0107] As used herein, the term "substantially" with respect to a particular composition and / or solution and / or other parameter means at least about 50% and up to 100% of a unit or amount. As used herein, the term "significantly" with respect to a particular composition and / or solution and / or other parameter means at least about 75% and up to 100% of a unit or amount. As used herein, the term "substantially" with respect to a particular composition and / or solution and / or other parameter means at least about 90, 95, 98, or 99%, and up to 100% of a unit or amount. As used herein, the term "minor" with respect to a particular composition and / or solution and / or other parameter means at least about 1, 2, 4, or 10% and up to about 20, 30, 40, or 50% of a unit or amount.

[0108] It should be understood that like reference numerals in the drawings represent like elements throughout the several views, and that not all components and / or steps described and illustrated in connection with the figures are required in all embodiments or arrangements. Further, the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. The terms "including", "comprising", "having", "containing", "involving", and variations thereof as used herein, when used, specify the presence of the stated feature, integer, step, operation, element, and / or component, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or groups thereof.

[0109] The use of terms such as "first", "second", "third", etc. in the claims to modify elements of the claims does not by itself imply any priority, precedence, or order of one claim element over another claim, or the temporal order in which acts of a method are performed, but is used merely as a label to distinguish one claim element having a particular name from another element having the same name (ordinary terms apart) for the purpose of distinguishing claim elements.

[0110] In particular, the figures and the above embodiments do not mean to limit the scope of the present disclosure to a single embodiment, since other realizations are possible through the exchange of some or all of the described or illustrated elements. Further, if a particular element of the present disclosure can be partially or fully realized using known components, only such parts of the known components as are necessary for an understanding of the present disclosure are described, and detailed descriptions of other parts of such known components are omitted so as not to obscure the present disclosure. In this specification, embodiments showing a single component do not necessarily have to be limited to other embodiments including a plurality of the same components, unless otherwise explicitly stated herein, and vice versa. Further, the applicant does not intend to ascribe any non - general or special meaning to any term in this specification or claims, unless explicitly stated otherwise. Further, the present disclosure includes current and future known equivalents to the known components referred to herein by way of example.

[0111] The foregoing description of specific embodiments will make the general nature of the present disclosure very fully apparent, such that various applications of such specific embodiments can be readily modified and / or applied by those skilled in the relevant art, without departing from the general concepts of the present disclosure and without undue experimentation. Accordingly, such applications and modifications are to be considered within the meaning and scope of equivalents of the disclosed embodiments, based on the teachings and guidance presented herein. The language or terminology of this specification is for the purpose of explanation and not limitation, and thus it is to be understood that the terms or language of this specification are to be interpreted by those skilled in the art in light of the teachings and guidance presented herein, in combination with the knowledge of those skilled in the relevant art. It is to be understood that the dimensions discussed or shown are drawn according to one embodiment and that other dimensions can be used without departing from the present disclosure.

[0112] The foregoing objects are provided by way of example only and should not be construed as limiting. Various modifications and changes can be made to the subject matter described herein without departing from the true spirit and scope of the disclosure defined by and by several of the recitations in the following claims and by the structures and functions or steps that are equivalents of these recitations, without following the exemplary embodiments and applications illustrated and described.

[0113]

Table 1

[0114]

Table 2

[0115]

Table 3

[0116]

Table 4

Explanation of Reference Numerals

[0117] 10 Parent CMM 12 Oligomer CMM Unit 14 Supramolecular Template Molecule, Surfactant 16 Micelle 18 HOCMM 20 Mesopore 22 Micropore 100 Bragg Reflection Peak 200 Bragg Reflection Peak 211 Co - continuous Gyroid (Cubic) Reflection, Bragg Reflection 220 Co - continuous Gyroid (Cubic) Reflection, Bragg Reflection 321 Co - continuous Gyroid (Cubic) Reflection, Bragg Reflection 332 Co - continuous Gyroid (Cubic) Reflection, Bragg Reflection 211 co - continuous gyroidal (cubic) reflection, Bragg reflection 220 co - continuous gyroidal (cubic) reflection, Bragg reflection 321 co - continuous gyroidal (cubic) reflection, Bragg reflection 332 co - continuous gyroidal (cubic) reflection, Bragg reflection 400 co - continuous gyroidal (cubic) reflection, Bragg reflection 420 co - continuous gyroidal (cubic) reflection, Bragg reflection

Claims

1. A method for synthesizing a hierarchically ordered crystalline microporous material having a high degree of long-range mesoporous order by decomposing / cleaving a crystalline microporous material into its oligomeric components and reorganizing it into a hierarchically ordered mesostructure, A step of mixing a crystalline microporous material having a microporous structure, an alkaline reagent, and a supramolecular template to form an aqueous suspension, wherein the alkaline reagent is provided at a concentration of 0.1 to 5% by mass in the aqueous suspension and is selected from the group consisting of ammonia, ammonium hydroxide, and urea. The aqueous suspension is subjected to hot water treatment at 110 to 250°C for 12 to 96 hours to (a) form oligomer units of the crystalline microporous material, (b) form molded micelles of the supramolecular template, and (c) assemble the oligomer units around the molded micelles. A solid is formed as the hierarchical ordered mesostructure having a highly long-range mesoporous order with repeating mesopore periodicity over a length greater than 50 nm, and having pores characterized by crystalline microporous walls that maintain the microporous structure. The supramolecular template contains one or more bulk groups having dimensions based on the modeling of molecular dimensions as a rectangular parallelepiped having dimensions A, B, and C using van der Waals radii for each individual atom. A method wherein one or more, two or more, or all three of dimensions A, B, and C are sufficiently close to or sufficiently large in size with respect to the micropores of the crystalline microporous material, the micropores of the crystalline microporous material restrict diffusion into the micropores of the crystalline microporous material, and the dimensions relate to the head group of the surfactant, the tail group of the surfactant, or the co-template. method.

2. The method according to claim 1, wherein the aqueous suspension further comprises an ionic eusolute other than the anions associated with the supramolecular template, and the shape of the micelles is adjusted by selection of the supramolecular template and the ionic eusolute.

3. The ionic cosolute is CO 3 2- 、SO 4 2- 、S 2 O 3 2- 、H 2 PO 4 - 、F - 、Cl - 、Br - 、NO 3 - 、I - 、ClO 4 - 、SCN - 、and C 6 H 5 O 8 -3 The method according to claim 2, selected from the group consisting of

4. The aforementioned ionic cosolute is SO 4 2- NO 3 - , and Fiat 4 - The method according to claim 2, selected from the group consisting of the following.

5. The aforementioned ionic eusolute is NO 3 - The hierarchical ordered mesostructure possesses cubic mesophase symmetry, and the mesophase transition is characterized by a surfactant packing parameter g in the range of 0.4 to 0.8, where g = V / a 0 l And in the formula, V = Total volume of the surfactant tail of the supramolecular template, a 0 = Area of ​​the head group of the supramolecular template, and l = length of the surfactant tail of the supramolecular template That is, The method according to claim 2.

6. The method according to claim 2, wherein the ionic cosolute contains NO3-, the hierarchical ordered mesostructure has cubic meso-symmetry, and the molar ratio of the supramolecular template to the cosolute is in the range of 0.8 to 1.

3.

7. The ionic eusolute is SO 4 2- The hierarchical ordered mesostructure possesses hexagonal mesophase symmetry, and the mesophase transition is characterized by a surfactant packing parameter g in the range of 0.4 to 0.

6. g=V / a 0 l And in the formula, V = Total volume of the surfactant tail of the supramolecular template, a 0 = Area of ​​the head group of the supramolecular template, and l = length of the surfactant tail of the supramolecular template The method according to claim 2.

8. The method according to claim 2, wherein the ionic cosolute contains SO₄²⁻, the hierarchical ordered mesostructure has hexagonal meso-symmetry, and the molar ratio of the supramolecular template to the cosolute is in the range of 0.8 to 1.

3.

9. The ionic eusolute is ClO 4 - The hierarchical ordered mesostructure possesses lamellar mesophase symmetry, and the mesophase transition is characterized by a surfactant packing parameter g in the range of 0.9 to 1.

1. g=V / a 0 l And in the formula, V = Total volume of the surfactant tail of the supramolecular template, a 0 = Area of ​​the head group of the supramolecular template, and l = length of the surfactant tail of the supramolecular template The method according to claim 2.

10. The method according to claim 2, wherein the ionic eusolute contains ClO 4-, the hierarchical ordered mesostructure has lamellar meso-phase symmetry, and the molar ratio of the supramolecular template to the eusolute is in the range of 0.2 to 0.

7.

11. The method according to claim 1, wherein the supramolecular template contains at least one cationic moiety selected from the group consisting of a quaternary ammonium moiety and a phosphonium moiety.

12. The method according to claim 1, wherein the supramolecular template contains at least one quaternary ammonium group having a terminal alkyl group having 6 to 24 carbon atoms.

13. The method according to claim 1, wherein the supramolecular template contains two quaternary ammonium groups, and the alkyl group bridging the quaternary ammonium groups contains 1 to 10 carbon atoms.

14. The method according to claim 1, wherein the supramolecular template contains one or more bulk groups as a head group or tail group, selected from the group consisting of organosilanes, hydroxysilyls, alkoxysilyls, aromatics, branched alkyls, sulfonates, carboxylates, phosphates, and combinations of one of the aforementioned parts.

15. The method according to claim 14, wherein the supramolecular template contains at least one cationic moiety selected from the group consisting of a quaternary ammonium moiety and a phosphonium moiety.

16. The method according to claim 14, wherein the supramolecular template contains at least one quaternary ammonium group having a terminal alkyl group having 6 to 24 carbon atoms.

17. The method according to claim 14, wherein the supramolecular template contains two quaternary ammonium groups, and the alkyl group bridging the quaternary ammonium groups contains 1 to 10 carbon atoms.

18. The method according to claim 1, wherein the supramolecular template contains at least one quaternary ammonium group and at least one organosilane as a head group portion.

19. The method according to claim 1, wherein the supramolecular template contains at least one quaternary ammonium group and at least one head group portion selected from the group consisting of combinations of organosilane, hydroxysilyl, alkoxysilyl, aromatic, branched alkyl, sulfonate, carboxylate, phosphate, and one of the aforementioned portions, and the alkyl group crosslinking at least one of the quaternary ammonium groups and at least one of the head groups contains 1 to 10 carbon atoms.

20. The method according to claim 1, wherein the supramolecular template comprises dimethyloctadecyl(3-trimethoxysilyl-propyl)ammonium or a derivative of dimethyloctadecyl(3-trimethoxysilyl-propyl)ammonium.

21. The crystalline microporous material is characterized by pore channels, cavities, or window openings having pore dimensions, and further, if the crystalline microporous material is characterized by pore channels, cavities, or window openings having various dimensions, the pore dimensions are the largest among the pore channels, cavities, or window openings having various dimensions. The supramolecular template has dimensions that restrict the diffusion of the crystalline microporous material into the pore channels, cavities, or window openings having the aforementioned dimensions. A quaternary ammonium moiety, and a constituent group selected from the group consisting of organosilanes, hydroxysilyls, alkoxysilyls, aromatics, branched alkyls, sulfonates, carboxylates, phosphates, and combinations containing one of the aforementioned constituent groups; A quaternary phosphonium moiety, and a constituent group selected from the group consisting of organosilanes, hydroxysilyls, alkoxysilyls, aromatics, branched alkyls, sulfonates, carboxylates, phosphates, and combinations of one of the aforementioned constituent groups; or Two quaternary ammonium groups, wherein the alkyl group bridging the quaternary ammonium groups contains 1 to 10 carbon atoms, The method according to claim 1, comprising one or more of the following.

22. The method according to any one of claims 1 to 21, wherein the alkaline reagent is urea, and during the hot water treatment, the urea reacts to form ammonium hydroxide, thereby controlling the hot water treatment.

23. The method according to any one of claims 1 to 21, wherein the hierarchical ordered mesostructure is calcined in its formed state, and the calcination reduces the amorphous content of the hierarchical ordered mesostructure.

24. The method according to any one of claims 1 to 21, wherein the crystalline microporous material includes a zeolite or a zeolite-type material selected from the group consisting of aluminophosphate (AlPO), silicon-substituted aluminophosphate (SAPO), metal-containing aluminophosphate (MAPO), and zeolite-based silicon-containing skeletal materials.

25. The method according to any one of claims 1 to 21, wherein the crystalline microporous material is a zeolite having a framework selected from the group consisting of AEI, *BEA, CHA, FAU, MFI, MOR, LTL, LTA, and MWW.

26. The method according to any one of claims 1 to 21, wherein the crystalline microporous material is a zeolite having a FAU framework.

27. ​​The method according to claim 1, wherein the crystalline microporous material is a zeolite having a FAU skeleton, the supramolecular template is a quaternary ammonium moiety including a head containing a terminal alkyl group having 6 to 24 carbon atoms and a portion selected from the group consisting of organosilane, hydroxysilyl and alkoxysilyl, and the supramolecular template has dimensions that restrict diffusion into the micropores of the crystalline microporous material.

28. The supramolecular template is Dimethyloctadecyl(3-trimethoxysilylpropyl)ammonium is the cation paired with an anion selected from the group consisting of Cl-, Br-, OH-, F-, and I-; [2,3-bis(dodecanoyloxy)-propyl](3-(trimethoxysilyl)propyl)-dimethylammonium is the cation paired with an anion selected from the group consisting of Cl-, Br-, OH-, F-, and I-. Dimethylhexadecyl(3-trimethoxysilylpropyl)ammonium is the cation paired with an anion selected from the group consisting of Cl-, Br-, OH-, F-, and I-. The method according to claim 27.

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