Hierarchical ordered crystalline microporous material with long-range mesoporosity having lamellar symmetry

Abstract

A composition is provided that includes a hierarchical ordered crystalline microporous material having lamellar symmetric defined long-range mesoporous order. The composition possesses mesopores having the walls of the crystalline microporous material and a group of mesostructures between the mesopores of the crystalline microporous material. The long-range order is defined by the presence of secondary peaks in an X-ray diffraction (XRD) pattern and / or lamellar symmetry observable by microscopy.

Description

Technical Field

[0001] The present disclosure relates to hierarchical ordered crystalline microporous materials.

Background Art

[0002] Zeolites are microporous aluminosilicate materials having 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 controlled porosity and other properties, and typically contain cations, water, and / or other molecules located in the porous network. Hundreds of natural and synthetic zeolite frameworks exist in a wide range of applications. Many zeolites occur naturally and are mined extensively, and a large amount of interdependent research has led to synthetic zeolites of a rich variety of structures and compositions. The unique properties of zeolites and the ability to tailor zeolites for specific applications have led to the widespread use of zeolites in industry as catalysts (e.g., for 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 have acidity levels that enhance their effectiveness as catalyst materials or adsorbents, either alone or by addition of active components. Only one of the hundreds of types of zeolites clarified by the International Zeolite Association (IZA) will be described below. 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 producing 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 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] While zeolites have found great utility in their 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 on 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] An attractive property of ordered structures is that their architecture can be described in terms of their symmetry. A well-defined crystal is associated with a well-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 distinct 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 that have fewer dimensions than 3D, there are four crystal systems: hexagonal, square, rectangular, and orthorhombic.

[0007] 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 discriminate 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 that they are prone to coking, which can lead to accelerated catalyst deactivation and product selectivity.

[0008] In this regard, hierarchically ordered zeolites (HOZs) with 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 Bronsted 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 processing. 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 zeolites 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 Document

[0011]

Patent Document 1

Non-Patent Document

[0012]

Non-Patent Document 1

Non-Patent Document 2

Non-Patent Document 3

Non-Patent Document 4

[0013] In view of the conventional attempts to generate hierarchically ordered zeolites, hierarchically ordered zeolites are 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 a composition of hierarchically ordered zeolites having a defined long-range mesoporous order with lamellar symmetry.

Means for Solving the Problems

[0014] Compositions are provided that include a crystalline microporous material such as a hierarchically ordered zeolite or zeolite-type material. These hierarchically ordered crystalline mesoporous materials have a defined long-range mesoporous order with lamellar symmetry, including mesopores having walls of the crystalline microporous material and a group of mesostructures between the mesopores composed of the crystalline microporous material. The long-range order is defined by the presence of secondary peaks in the X-ray diffraction (XRD) pattern and / or the presence of lamellar symmetry observable by microscopy.

[0015] In certain embodiments, the composition includes a hierarchically ordered crystalline microporous material having a defined long-range mesoporous order with lamellar symmetry, including a group of mesostructures between mesopores having walls composed of the crystalline microporous material and the mesopores of the crystalline microporous material. At least a portion of the mesopores contain micelles of a supramolecular template shaped to induce a lamellar symmetric mesoporous order. The supramolecular template has one or more dimensions larger than the dimensions of the micropores of the crystalline microporous material so as to limit diffusion into the micropores of the crystalline microporous material, and this dimension is related to the head group of the supramolecular template, the tail group of the supramolecular template, or the co-template arrangement configuration that limits diffusion into the micropores of the crystalline microporous material. In certain embodiments, an ionic cosolute is present in the hierarchically ordered crystalline microporous material; in certain embodiments, the ionic cosolute includes ClO4 - and.

[0016] In certain embodiments, the lamellar mesophase has p2 or p1 or pm symmetry. In certain embodiments, the lamellar mesophase has p2 symmetry and the secondary peak in XRD is present at the (200) reflection. In certain embodiments, the long-range order is observable by microscopy looking at an electron beam parallel or perpendicular to the

[0100] zone axis.

[0017] In certain embodiments, the parent crystalline microporous material includes a zeolite or a zeolite-type material. For example, the parent 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. In certain embodiments, the parent crystalline microporous material is a zeolite having a FAU framework.

[0018] In certain embodiments, there is provided a hydrocracking catalyst comprising a hierarchical ordered zeolite described herein, an inorganic oxide as a binder, and an active metal component. For example, the hierarchical ordered crystalline microporous material comprises the hydrocracking catalyst in an amount of about 0.1 to 99, 0.1 to 90, 0.1 to 80, 0.1 to 70, 0.1 to 50, 0.1 to 40, 2 to 99, 2 to 90, 2 to 80, 2 to 70, 2 to 50, 2 to 40, 20 to 100, 20 to 90, 20 to 80, 20 to 70, 20 to 50, or 20 to 40 mass%. The inorganic oxide component is selected from the group consisting of 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. In certain embodiments, the inorganic oxide component comprises alumina. In certain embodiments, the zeolite comprises FAU zeolite. In certain embodiments, the active metal component comprises one or more of Mo, W, Co, or Ni (oxide or sulfide). The active metal component comprises one or more metals selected from Groups 6, 7, 8, 9, or 10 of the IUPAC Periodic Table of the Elements.

[0019] Any combination of the various embodiments and realizations disclosed in this specification can be used. These and other aspects and features can be understood from the following description of a particular embodiment, the accompanying drawings, and the claims.

[0020] 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

[0021]

Figure 1

Figure 2

Figure 3A

Figure 3B

Figure 4A

Figure 4B

Figure 4C

Modes for Carrying Out the Invention

[0022] Compositions are provided that include hierarchically ordered crystalline microporous materials (“CMMs”). These hierarchically ordered crystalline microporous materials (“HOCMMs”) have a lamellar symmetric defined long-range mesoporous order that includes mesopores having a group of mesostructures between the walls of the crystalline microporous material and the mesopores of the CMM. The long-range ordering is defined by the presence of secondary peaks in the X-ray diffraction (XRD) pattern and / or the lamellar symmetry observable by microscopy. In certain embodiments, for example, prior to calcination of the synthesized HOCMM, at least a portion of the mesopores contain micelles of a supramolecular template shaped to induce a lamellar symmetric mesoporous order, and this supramolecular template maintains one or more dimensions larger than the dimensions of the micropores of the crystalline microporous material so as to limit diffusion into the micropores of the crystalline microporous material. The dimensions relate to the head group of the supramolecular template, the tail group of the supramolecular template, or the co-template arrangement configuration that limits diffusion into the micropores of the CMM. The HOCMM is synthesized by using base-mediated reassembly, by decomposition of 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 methods herein having a lamellar symmetric mesoporous order, including embodiments using ionic co-solutes. The method for obtaining a composition including what is disclosed herein is disclosed in U.S. Patent Application No. 17 / 857,671, filed July 5, 2022, entitled “Methods for Synthesis of Hierarchically Ordered Crystalline Microporous Materials with Long-Range Mesoporous Order,” which is co-pending and commonly owned and is incorporated herein by reference.

[0023] In certain embodiments for the reassembly to generate the compositions of the present specification: The rate and extent of CMM degradation are controlled by using urea as a base in situ and mediating the hot water temperature to control the hydrolysis of urea and finely tune 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, i.e., the anionic Hofmeister effect (AHE) on supramolecular self-assembly, governs the formation of hierarchical ordered structure lamellar symmetry; in certain embodiments, the hierarchical ordered structure maintains lamellar p2 symmetry.

[0024] According to embodiments of the method for generating the compositions of the present specification, the parent CMM is formed in an aqueous suspension by an alkaline reagent and a supramolecular templating agent. In additional embodiments, 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 to oligomeric units of CMM with very few monomer units and hierarchical reassembly of the oligomeric units into mesostructures. The conditions of the system (including the temperature and time of crystallization), the choice and concentration of the supramolecular template, and the choice and concentration of the alkaline reagent are adjusted to control the cleavage of the parent CMM to oligomeric units and the reassembly of those oligomeric units around the shape of the supramolecular template micelles. The degradation of the parent CMM is promoted to an extent of oligomer formation while minimizing monomer formation, which is controlled by the choice of supramolecular template, alkaline reagent, ionic co-solute if necessary, and hot water 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 of CMM or atomic constituents. In certain embodiments, the dimensions of the oligomeric units approximately correspond to the wall thickness of the synthesized mesoporous structure, 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 an ionic co-solute and Hofmeister effect if necessary.

[0025] Under effective crystallization conditions and times, and using effective types of supramolecular templates and alkaline reagents at effective relative concentrations, hierarchical ordering by the ensemble occurs after synthesis: the parent CMM is clipped into oligomeric CMM units that are repositioned around the shaped micelles formed by the supramolecular template. Hierarchically ordered CMMs with defined long-range mesoporous order are formed by a supramolecular templating method 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 supramolecular templates of the type / characteristics disclosed herein, followed by reorganization around defined micelles by supramolecular templating to form a hierarchically ordered structure with defined long-range lamellar mesoporous order.

[0026] The curvature or shape of the micelles results in the final lamellar mesophase symmetry. The formation of the supramolecular template molecules into micelles depends on factors such as the type of supramolecular template, the concentration of the supramolecular template, the presence or absence of ionic co-solutes, the type of CMM, the crystallization temperature, the type of alkaline reagent, the concentration of the alkaline 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. The hydrophobic interactions in a system containing a supramolecular template can vary the packing shape of the supramolecular template into, for example, spherical, oblate, or cylindrical micelles, and then form a thermodynamically stable two-dimensional or three-dimensional liquid crystal phase of an ordered mesostructure (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).

[0027] 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 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 maintain various polarizabilities, charge densities, and hydration energies in aqueous solutions. When paired with positive supramolecular template headgroups, these properties can affect short-range electrostatic repulsion in the headgroups and hydration at the micelle interface, and thus change the headgroup area (a0). Such ion-specific interactions can be the driving force in the change of micelle curvature and the induction of 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, while weakly hydrated ions can decrease micelle curvature. The surfactant packing parameter, g = V / a0l (V = total volume of the surfactant tail, a0 = headgroup area, l = length of the surfactant tail) can be used to describe these mesophase transitions.

[0028] 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 the hydroxide of sodium, lithium, potassium, rubidium, or cesium.

[0029] In certain embodiments, the alkaline reagent is effective to allow for controlled hydrolysis; for example, urea can be used as an alkaline agent and during hydrolysis, urea reacts to form ammonium hydroxide. 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 to the process.

[0030] 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 -It can be a counter anion. In certain embodiments, the alkali reagent contains 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 template.

[0031] 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 the apparent amorphous material present is reduced (e.g., a broad band overall at 25° (2θ) in XRD), which indicates an apparent "self-healing" after calcination. In certain embodiments, when directly compared with an alternative route such as NaOH or ammonium hydroxide, the amount of the apparent amorphous material present in the HOCMM is reduced by the controlled hydrolysis of urea to ammonium hydroxide (e.g., a broad band overall at 25° (2θ) in XRD).

[0032] In a method for synthesizing a hierarchical ordered CMM having a defined long-range mesoporous order disclosed herein, a suitable surfactant as a supramolecular template is provided to assist in the reassembly and recrystallization of the decomposition components (oligomers) by shared and / or electronic valence interactions. The supramolecular template is provided at a concentration in an aqueous suspension of about 0.01 - 0.5 M. In certain embodiments, a suitable supramolecular template is provided at a concentration in an aqueous suspension of about 0.5 - 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. The 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 the diffusion or partial diffusion thereof into the CMM pore-channels, cavities, or window openings. Such a supramolecular template maintains 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 a template system arranged 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 aromatic or aromatic derivative groups (> about 0.6 nm). In certain embodiments, the supramolecular template contains one or more bulk-like groups having dimensions based on modeling of molecular dimensions as a rectangular parallelepiped having dimensions A, B, and C using van der Waals radii for each individual atom, and one or more, two or more, or all three of dimensions A, B, and C are of a size that is close enough or large enough in size to limit diffusion into the micropores of the selected parent CMM.

[0033] In certain embodiments, surfactants effective as supramolecular templates contain 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, an effective supramolecular template is an organosilane containing at least one hydroxysilyl as a head group moiety. In certain embodiments, an effective supramolecular template is an organosilane containing at least one hydroxysilyl as a tail group moiety. In certain embodiments, an effective supramolecular template is an organosilane containing at least one alkoxysilyl as a head group moiety. In certain embodiments, an effective supramolecular template is an organosilane containing at least one alkoxysilyl as a tail group moiety. In certain embodiments, an effective supramolecular template contains at least one aromatic as a head group moiety. In certain embodiments, an effective supramolecular template contains at least one aromatic as a tail group moiety. In certain embodiments, an effective supramolecular template contains at least one branched alkyl as a head group moiety. In certain embodiments, an effective supramolecular template contains at least one branched alkyl as a tail group moiety. In certain embodiments, an effective supramolecular template contains at least one sulfonate as a head group moiety. In certain embodiments, an effective supramolecular template contains at least one sulfonate as a tail group moiety. In certain embodiments, an effective supramolecular template contains at least one carboxylate as a head group moiety. In certain embodiments, an effective supramolecular template contains at least one carboxylate as a tail group moiety. In certain embodiments, an effective supramolecular template contains at least one phosphate as a head group moiety. In certain embodiments, an 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 features pores of various dimensions, the selected portion features one or more dimensions that limit diffusion into the largest pores of the parent CMM.

[0034] 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.

[0035] In certain embodiments, an effective supramolecular template comprises a quaternary ammonium compound and a structural group comprising one or more bulky 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.

[0036] In certain embodiments, an effective supramolecular template comprises a quaternary phosphonium compound and a structural group comprising one or more bulky aromatic substituents. In certain embodiments, an effective supramolecular template comprises a quaternary phosphonium compound and a structural group comprising one or more bulky alkoxysilyl or organic silane substituents.

[0037] In certain embodiments, an effective supramolecular template contains a tail group portion selected from the group consisting of an aromatic group containing 6 to 50, 6 to 25, 10 to 50, or 10 to 25 carbon atoms, an alkyl group containing 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 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 6 to 50, 6 to 25, 10 to 50, or 10 to 25 carbon atoms, an alkyl group containing 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 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.

[0038] In certain embodiments, effective supramolecular templates are: (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, effective supramolecular templates include a sulfonate group (non-limiting examples are sulfonated bis(2-hydroxy-5-dodecylphenyl)methane (SBHDM)). In certain embodiments, effective supramolecular templates include a carboxylate group (non-limiting example is sodium 4-(octyloxy)benzoate). In certain embodiments, effective supramolecular templates include a phosphonate group (non-limiting example is tetradecyl(1,4-benzene)bisphosphonate). In certain embodiments, effective supramolecular templates include an aromatic group (non-limiting example is cetyl dimethyl benzyl ammonium chloride). In certain embodiments, effective supramolecular templates include an aliphatic group (non-limiting example is tetraoctylammonium chloride).

[0039] Supramolecular templates are provided as cation / anion pairs. In certain embodiments, the cation of the supramolecular template is as described above, and pairs with a selected anion such as Cl - , Br - , OH - , F - , and I - . 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 comprises 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 comprises dimethylhexadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, or a derivative of dimethylhexadecyl[3-(trimethoxysilyl)propyl]ammonium chloride. In certain embodiments, an effective supramolecular template comprises [2,3-bis(dodecanoyloxy)-propyl](3-(trimethoxysilylyl)propyl)-dimethylammonium iodide, or a derivative of [2,3-bis(dodecanoyloxy)-propyl](3-(trimethoxysilyl)propyl)-dimethylammonium iodide.

[0040] In certain embodiments, the system comprises 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 selected based on the Hofmeister series / lyotropic series to control the curvature / shape of the micelles to achieve the desired lamellar mesophase symmetry. In certain embodiments, perchlorate (ClO4 -) is an ionic cosolute selected based on the Hofmeister series / lyotropic series so as to control the curvature / shape of the micelles, resulting in a hierarchical ordered CMM having a defined long-range mesoporous order that preserves the lamellar meso symmetry; in certain embodiments, where perchlorate is used as the ionic cosolute, perchlorates 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.

[0041] 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 high-quality HOCMMs while maintaining composite phases and / or impurities.

[0042] Zeolite materials suitable as parent CMMs are 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, for example, a (FAU) framework zeolite including USY having a micropore diameter related to a 12-membered ring when viewed along the

[0111] direction of, for example, 7.4×7.4 Å. In certain embodiments, the parent zeolite can be, for example, a (MFI) framework zeolite including ZSM-5 having micropore diameters related to 10-membered rings when 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, for example, a (MOR) framework zeolite including mordenite zeolite having micropore diameters related to 12-membered and 8-membered rings when 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, a zeolite beta polymorph A having a micropore diameter related to a 12-membered ring when 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 when viewed perpendicular to the

[0001] direction of "interlayer" and "intralayer" of 4.0×5.5 Å and 4.1×5.1 Å, respectively.

[0043] 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.

[0044] 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, where one or more, two or more, or all three of dimensions A, B, and C have dimensions that are close enough or large enough that they limit diffusion into the micropores of the CMM. Also, as already mentioned 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 limited. Similarly, a suitable supramolecular template is determined based on the selected parent CMM.

[0045] 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 be in the range of about 2 to 10000, 2 to 5000, from 2 to 500, from 2 to 100, from 2 to 80, from 5 to 10000, from 5 to 5000, from 5 to 500, from 5 to 100, from 5 to 80, from 10 to 10000, from 10 to 5000, from 10 to 500, from 10 to 100, from 10 to 80, from 50 to 10000, from 50 to 5000, from 50 to 1000, from 50 to 500, or from 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.

[0046] Figures 1 and 2 are schematic diagrams of a method for making the compositions disclosed herein that use hierarchical ordering by a post-synthetic ensemble synthesis pathway, including a general synthetic mechanism of how AHE affects the g-value to vary the curvature of micelles and induce a mesophase transition. The CMMs schematically shown in Figures 1 and 2 are FAU zeolites, although it is understood that other CMMs can be utilized as the parent CMMs to form the compositions herein by a post-synthetic ensemble synthesis pathway.

[0047] 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 alkali reagent and an effective amount of a surfactant are added with respect to 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 into shaped micelles 16, and the oligomeric CMM units hierarchically reassemble and crystallize around the shaped micelles to form an ordered mesostructure, HOCMM 18, having defined symmetric mesopores 20 and mesopore walls formed of oligomeric CMM units, thereby retaining the micropores 22 of the CMM structure underlying the parent CMM. In certain embodiments, the composition herein is an HOCMM 18 containing shaped micelles 16. In certain embodiments, the composition herein is an HOCMM 18 having a surfactant 14 formed on the shaped micelles 16 that is removed by a chemical method such as, for example, solvent extraction, chemical oxidation, or ionic liquid treatment; or a physical method such as calcination, supercritical CO2, microwave-assisted treatment, ultrasonic-assisted treatment, ozone treatment, or plasma technology.

[0048] Referring particularly to FIG. 2, a schematic synthesis mechanism is shown that includes a schematic representation of the effect of AHE on the g-value and simultaneously on the micelle curvature and the induced mesophase transition. In certain embodiments, the perchlorate is used as an ionic co-solute, the micelle curvature is represented by a surfactant packing parameter g in the range of about 1, and the resulting HOCMM maintains a lamellar symmetric long-range mesoporous order. The ion-specific interaction (Hofmeister effect) on the micelle curvature in the self-assembly process is evident. Anions of various sizes and charges maintain 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 at the micelle interface, and thus change the head group area (a0). Such short-range ion-specific interactions can be a significant driving force in changing the micelle curvature and inducing a mesophase transition. Based on the Hofmeister series (SO4 2- > HPO4 2- > OAc - > Cl - > Br - > NO3 - > ClO4 - > SCN - ), strongly hydrated ions (left side of the series) can increase the micelle curvature, whereas weakly hydrated ions can reduce the micelle curvature.

[0049] An effective amount of a 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 co-solvent selected from the group consisting of polar solvents, non-polar 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, non-polar 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 enables 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 more closely match those of the adjacent crystals. Insufficient mixing can lead to an undesirable product with an amorphous phase or a lower degree of long-range order.

[0050] 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 vessel prior to heating), in an autoclave, or in another suitable vessel with agitation, rolling, and / or shaking, etc. The mixing of the suspension components is carried out at a temperature between about 20 to 60, 20 to 50, or 20 to 40 °C.

[0051] The cutting and reassembly steps are carried out during the hydrothermal treatment to form solids (products, HOCMMs with a defined long-range mesoporous order of 2D-lamellar symmetry) 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 150, 90 to 250, 90 to 210, 90 to 180, 90 to 150, 110 to 250, 110 to 210, 110 to 180, 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.

[0052] The HOCMMs with a defined long-range mesoporous order of 2D-lamellar symmetry are the products to be recovered. The solids are recovered using known techniques such as centrifugation, decantation, gravity, vacuum filtration, filter press, or rotary drum. The recovered HOCMMs with a defined long-range mesoporous order of 2D-lamellar symmetry are 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 about 0.5 to 96, 12 to 96, or 24 to 96 hours.

[0053] In certain embodiments, the dried HOCMM having a defined long-range mesoporous order of 2D-lamellar symmetry is calcined to remove, for example, the supramolecular template remaining in the mesophase and other constituents from mesopores and / or individual zeolite cell micropores. Conditions for calcination of the embodiments carried out 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. 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, 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.

[0054] In certain embodiments, the supernatant remaining after recovering the product from the system is recovered and all or a portion thereof can be reused as all or a portion of the solution in a subsequent process for synthesizing an HOCMM or another HOCMM having a defined long-range mesoporous order of 2D-lamellar symmetry. 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.

[0055] The compositions recovered as described herein are hierarchical ordered CMMs (such as zeolites) having a defined long-range mesoporous order with 2D-lamellar symmetry. These are characterized by the mesoporous channel direction defined by the CMM micropore channels within the walls of the mesostructure. The HOCMMs having a defined long-range mesoporous order with 2D-lamellar symmetry, recovered from synthesis, retain the supramolecular templates described herein within the mesopores (i.e., prior to calcination or extraction of the supramolecular template). In certain embodiments, the HOCMMs having a defined long-range mesoporous order, recovered from synthesis, retain micelles of the supramolecular templates described herein within the mesopores (i.e., prior to calcination or extraction of the supramolecular template). 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 having a defined mesoporous 2D-lamellar symmetry.

[0056] 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 the mesopores in the x-ray diffraction (XRD) pattern for a given mesophase, as demonstrated in the examples herein, and / or by microscopic observations. These peaks associated with the mesoporous properties of the product are observed at low 2θ angles. The material also shows high-angle peaks associated with the zeolite, 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°.

[0057] In certain embodiments herein, the long-range mesoporous order of the HOCMMs produced by the methods described herein is characterized by the periodicity of the mesopores repeating over lengths greater than about 50 nm.

[0058] In certain embodiments, the HOCMM having the defined long-range mesoporous order of 2D-lamellar symmetry herein has a surface area of about 200 - 1500, 200 - 1000, 200 - 900, 400 - 1500, 400 - 1000, 400 - 900, 500 - 1500, 500 - 1000, or 500 - 900 m² / g. In embodiments herein, the HOCMM having the defined long-range mesoporous order of 2D-lamellar symmetry herein has a mesoporous pore diameter of about 2 - 50, 2 - 20, or 2 - 10 nm. In embodiments herein, the HOCMM having the defined long-range mesoporous order of 2D-lamellar symmetry herein has a silica to alumina ratio of about 2.5 - 1500, 3 - 1500, 4 - 1500, 5 - 1500, 6 - 1500, 2.5 - 1000, 3 - 1000, 4 - 1000, 5 - 1000, 6 - 1000, 2.5 - 500, 3 - 500, 4 - 500, 5 - 500, 6 - 500, 2.5 - 100, 3 - 100, 4 - 100, 5 - 100, or 6 - 100. In embodiments herein, the HOCMM having the defined long-range mesoporous order of 2D-lamellar symmetry herein has a total pore volume of about 0.01 - 1.50, 0.01 - 1.0, 0.01 - 0.75, 0.01 - 0.65, 0.1 - 1.50, 0.1 - 1.0, 0.1 - 0.75, 0.1 - 0.65, 0.2 - 1.50, 0.2 - 1.0, 0.2 - 0.75, 0.2 - 0.65, 0.3 - 1.50, 0.3 - 1.0, 0.3 - 0.75, or 0.3 - 0.65 cc / g. 2 / g. In embodiments herein, the HOCMM having the defined long-range mesoporous order of 2D-lamellar symmetry herein has a mesoporous pore diameter of about 2 - 50, 2 - 20, or 2 - 10 nm. In embodiments herein, the HOCMM having the defined long-range mesoporous order of 2D-lamellar symmetry herein has a silica to alumina ratio of about 2.5 - 1500, 3 - 1500, 4 - 1500, 5 - 1500, 6 - 1500, 2.5 - 1000, 3 - 1000, 4 - 1000, 5 - 1000, 6 - 1000, 2.5 - 500, 3 - 500, 4 - 500, 5 - 500, 6 - 500, 2.5 - 100, 3 - 100, 4 - 100, 5 - 100, or 6 - 100. In embodiments herein, the HOCMM having the defined long-range mesoporous order of 2D-lamellar symmetry herein has a total pore volume of about 0.01 - 1.50, 0.01 - 1.0, 0.01 - 0.75, 0.01 - 0.65, 0.1 - 1.50, 0.1 - 1.0, 0.1 - 0.75, 0.1 - 0.65, 0.2 - 1.50, 0.2 - 1.0, 0.2 - 0.75, 0.2 - 0.65, 0.3 - 1.50, 0.3 - 1.0, 0.3 - 0.75, or 0.3 - 0.65 cc / g.

[0059] In embodiments of the present specification, the products generated by the above method and demonstrated in the examples of the present specification are characterized by a high degree of long-range lamellar mesophase order. In certain embodiments, the product is a lamellar mesoporous zeolite with lamellar mesophase order. The HOCMM with a mesophase having lamellar symmetry is characterized by the lamellar mesoporous channel direction having CMM micropore channels in the walls of the mesostructure. In these embodiments, the CMM structure is arranged symmetrically in a lamellar pattern at the mesoscale, and these CMM particles (regardless of their atomic-level symmetry or structure) are arranged (at the mesoscale) around the micelles, thereby arranging micelles exhibiting lamellar symmetry. 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 as seen by an electron beam in a direction parallel or perpendicular to the

[0100] zone axis. Thus, the HOCMM having a lamellar mesophase includes CMMs characterized by atomic-level symmetry and having micropores inherent to that type of CMM, arranged symmetrically in a lamellar pattern at the mesoscale with respect to the mesopores, 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 those oligomers around micelles exhibiting lamellar symmetry at the mesoscale. In one embodiment, there is provided an HOCMM that includes an MFI zeolite having orthorhombic symmetry at the atomic level arranged in a lamellar symmetry at the mesoscale, wherein oligomers of the parent MFI zeolite are formed during the synthesis of the hierarchical ordered zeolite from the parent MFI zeolite and are 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 on a lamellar symmetric mesoscale. During the synthesis of the hierarchical ordered zeolite from the parent CHA zeolite, oligomers of the parent CHA zeolite are formed and arranged around micelles exhibiting lamellar 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 lamellar symmetric mesoscale. During the synthesis of the hierarchical ordered zeolite from the parent BEA zeolite, oligomers of the parent BEA zeolite are formed and arranged around micelles exhibiting lamellar 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 lamellar symmetric mesoscale. During the synthesis of the hierarchical ordered zeolite from the parent MWW zeolite, oligomers of the parent MWW zeolite are formed and arranged around micelles exhibiting lamellar 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 lamellar symmetric 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 exhibiting lamellar symmetry on the mesoscale.

[0060] 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 be exfoliated to form sheets of CMMs, such as zeolite nanosheets. In certain embodiments, CMMs such as the zeolitic crystalline structures arranged in lamellar symmetry provided herein can maintain the lamellar symmetry by using columnarization techniques known in the art. For example, a silica source such as tetraethyl orthosilicate (TEOS) condenses within the lamellar structure and crystallizes 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 maintain the mesoscale lamellar symmetry in a columnar or lamellar structure, they can be used, for example, as catalyst materials or catalyst support materials.

[0061] The HOCMMs produced according to the present disclosure are effective as catalysts or catalyst components in the hydrocracking of hydrocarbon oils in certain embodiments with a columnarized lamellar structure. The HOCMMs can be used as a support on which one or more active and durable 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 contains BEA, CHA, FAU, MFI, MOR, LTL, LTA, or MWW. In certain embodiments, the CMM of the HOCMM contains a FAU zeolite.

[0062] The contents of the HOCMM and the active metal component are appropriately determined according to the object. In certain embodiments, the hydrocracking catalyst contains the HOCMM as a carrier and typically an inorganic oxide component as a binder and / or 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 to 99, 0.1 to 90, 0.1 to 80, 0.1 to 70, 0.1 to 50, 0.1 to 40, 2 to 99, 2 to 90, 2 to 80, 2 to 70, 2 to 50, 2 to 40, 20 to 100, 20 to 90, 20 to 80, 20 to 70, 20 to 50, or 20 to 40 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 to 99, 0.1 to 90, 0.1 to 80, 0.1 to 70, 0.1 to 50, 0.1 to 40, 2 to 99, 2 to 90, 2 to 80, 2 to 70, 2 to 50, 2 to 40, 20 to 100, 20 to 90, 20 to 80, 20 to 70, 20 to 50, or 20 to 40 mass%, and the remaining content is an inorganic oxide and one or more other zeolite-based materials.

[0063] 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.

[0064] The active metal component can include one or more metals or metal compounds (oxides or sulfides) known in the art 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 included in the catalyst in effective concentrations. For example, the total active component content in the hydrocracking catalyst can be present in amounts known in the 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

[0065] 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 parent zeolites used in the examples and comparative examples have the FAU framework and zeolite Y (obtained from Zeolyst International, product name CBV 720) is referred to herein as zeolite H-Y and has an SAR of about 30. 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 from commercial manufacturers and from other sources and of other types described herein. Thus, the resulting compositions have a mesoporous structure with a microporosity corresponding to the parent CMM and a CMM structure.

[0066] 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 physical adsorption 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.

[0067] (Example 1A) A method for synthesizing 2D-lamellar ordered mesoporous FAU-type zeolite is provided. An amount of 1.2 grams of urea was dissolved in 60.0 g of water to form a homogeneous solution. To this mixture, 2.0 g of zeolite H-Y was added and stirred. 0.92 g of sodium perchlorate (NaClO4) was added and stirred for 10 minutes. Then, 3.0 milliliters of an organic silane, dimethyloctadecyl(3-trimethoxysilyl-propyl)-ammonium chloride (42.0 mass% in methanol) was added. The resulting solution was stirred for 0.5 hour, and then hydrothermal treatment was carried out 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 Y-U-C-TMS (where Y refers to zeolite Y, C refers to perchlorate, U refers to urea, and TMS refers to dimethyloctadecyl(3-trimethoxysilyl-propyl)-ammonium chloride). The structural and textural properties of Y-U-C-TMS are presented in Table 3.

[0068] (Example 1B) The procedure followed that of Example 3A except that an amount of 4.75 g of NH4OH was used as the alkali reagent instead of urea.

[0069] In Example 1A, the resulting hierarchical zeolite is a 2D-lamellar ordered mesoporous FAU-type 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 3A shows a low-angle XRD pattern, Figure 3B shows a high-angle XRD pattern, where "a" corresponds to commercial-USY (zeolite H-Y), and "b" corresponds to Y-U-C-TMS: Figures 4A to 4C are TEM micrographs of Y-U-C-TMS showing the lamellar structure; Figure 4A shows a TEM micrograph at a scale of 50 nanometers in the planar direction

[0100] ; Figure 4B shows a TEM micrograph at a scale of 20 nanometers; and Figure 4C shows a TEM micrograph at a scale of 50 nanometers in the planar direction

[0110] . The high degree of long-range order is evident from Figure 3A, where the low-angle XRD pattern shows Bragg reflections at peaks 100 and 200, suggesting 2D-lamellar (p2) mesopore symmetry. The retention of the underlying zeolite structure is evident from Figure 3B, where the high-angle XRD pattern is consistent with the pattern of the parent zeolite, the FAU zeolite.

[0070] According to the examples herein, the hierarchical ordered FAU-type framework showing 2D-lamellar (p2) mesopore symmetry is prepared for the first time by systematic post-synthesis reassembly.

[0071] 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 portion" 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.

[0072] 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 features, integers, steps, operations, elements, and / or components referred to, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or groups thereof.

[0073] The use of terms such as "first," "second," "third," etc. in a claim to modify elements of the claim does not, in itself, imply any priority, precedence, or order of elements of one claim over another claim, or the temporal order in which acts of a method are performed, but is merely used as a label to distinguish an element of one claim having a particular name from another element having the same name (apart from common terms) for distinguishing elements of the claim.

[0074] In particular, the figures and the above embodiments do not mean that the scope of the present disclosure is limited 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 realized partially or completely using known components, only those portions of such known components that are necessary for an understanding of the present disclosure are described, and detailed descriptions of other portions of such known components are omitted so as not to obscure the present disclosure. In this specification, an embodiment showing a single component does not necessarily have to be limited to other embodiments including a plurality of the same components, and vice versa, unless otherwise explicitly stated herein. Further, the applicant does not intend to ascribe an uncommon or special meaning to any term in this specification or the claims, unless such is explicitly stated. Further, the present disclosure includes current and future known equivalents to the known components referred to herein by way of example.

[0075] The foregoing description of specific embodiments will enable others skilled in the art to modify and / or apply various applications of such specific embodiments without undue experimentation and without departing from the general concepts of the present disclosure. Accordingly, such applications and modifications are intended to be within the meaning and scope of equivalents of the disclosed embodiments based on the teachings and guidance presented herein. The language or terminology used herein is for the purpose of description and not of limitation, and thus it should be understood that the terminology or language used herein is to be interpreted by those skilled in the art in light of the teachings and guidance presented herein in combination with their knowledge of the relevant art. It should 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.

[0076] The foregoing are provided merely as examples and are not to 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 invention as defined by the exemplary embodiments and applications illustrated and described herein, and without departing from the true spirit and scope of the present disclosure as defined by several of the recitations in the following claims and by the structures and functions or steps that are equivalents of these recitations.

[0077] [Table 1]

[0078] [Table 2]

[0079] [Table 3] [Explanation of Reference Numerals]

[0080] 10 Parent CMM 12 Oligomer CMM units 14 Supramolecular template molecules, surfactants 16 Micelles 18 HOCMM 20 Mesopores 22 Micropores

Claims

1. A hierarchically ordered crystalline microporous material having lamellar symmetric long-range mesoporous order, comprising mesopores having walls of the crystalline microporous material and a group of mesostructures between the mesopores of the crystalline microporous material, wherein the lamellar meso-symmetric long-range order is observable by microscopy, characterized by the presence of secondary peaks with a 2θ angle of less than 6° in the X-ray diffraction (XRD) pattern, and by repeating mesopore periodicity over lengths greater than 50 nm.

2. A hierarchically ordered crystalline microporous material having lamellar symmetric long-range mesoporous order, comprising mesopores having walls of the crystalline microporous material and a group of mesostructures between the mesopores of the crystalline microporous material, wherein at least a portion of the mesopores contains micelles of a supramolecular template shaped to induce lamellar symmetric mesoporous order, and the supramolecular template is sufficiently close to the dimensions of the micropores of the crystalline microporous material or the same dimensions as the micropores of the crystalline microporous material to restrict diffusion into the micropores of the crystalline microporous material. A material having one or more dimensions that are sufficiently larger than the dimensions of the micropores of a crystalline microporous material, wherein the dimensions relate to a head group of the supramolecular template, a tail group of the supramolecular template, or a co-template arrangement configuration that restricts diffusion into the micropores of the crystalline microporous material, and if the crystalline microporous material has pores of various dimensions, the one or more dimensions of the supramolecular template are sufficiently close to the largest micropore of the crystalline microporous material, or sufficiently larger than the largest micropore of the crystalline microporous material.

3. The hierarchically ordered crystalline microporous material according to claim 2, further comprising an ionic eusolute.

4. The ionic eusolute is ClO 4 - A hierarchically ordered crystalline microporous material according to claim 3, comprising:

5. The hierarchically ordered crystalline microporous material according to claim 1, wherein the lamellar mesophase has p2, p1, or pm symmetry.

6. The composition according to claim 1, wherein the lamellar mesophase has p2 symmetry and the secondary peak of the XRD is present at (200) reflection.

7. The hierarchically ordered crystalline microporous material according to claim 1, wherein the long-range order is observable by microscopy using electron beams parallel to or perpendicular to the [100] zone axis.

8. The hierarchically ordered crystalline microporous material according to any one of claims 1 to 7, 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 a zeolite-based silicon-only skeletal material.

9. The crystalline microporous material is AEI, * A hierarchically ordered crystalline microporous material according to any one of claims 1 to 7, which is a zeolite having a framework selected from the group consisting of BEA, CHA, FAU, MFI, MOR, LTL, LTA, and MWW.

10. The hierarchically ordered crystalline microporous material according to any one of claims 1 to 7, wherein the crystalline microporous material is a zeolite having a FAU framework.

11. A hydrocracking catalyst comprising a material, an inorganic oxide component as a binder, and an active metal component comprising one or more metals selected from group 6, 7, 8, 9, or 10 of the IUPAC periodic table, the hierarchically ordered crystalline microporous material according to claim 1 or any one of claims 5 to 7, which is a zeolite having a skeleton selected from the group consisting of AEI, *BEA, CHA, FAU, MFI, MOR, LTL, LTA, and MWW; an inorganic oxide component as a binder; and an active metal component comprising one or more metals selected from group 6, 7, 8, 9, or 10 of the IUPAC periodic table.

12. The hydrocracking catalyst according to claim 11, wherein the hierarchically ordered crystalline microporous material contains 0.1 to 99, 0.1 to 90, 0.1 to 80, 0.1 to 70, 0.1 to 50, 0.1 to 40, 2 to 99, 2 to 90, 2 to 80, 2 to 70, 2 to 50, 2 to 40, 20 to 100, 20 to 90, 20 to 80, 20 to 70, 20 to 50, or 20 to 40% by mass of the hydrocracking catalyst.

13. The hydrocracking catalyst according to claim 11, wherein the inorganic oxide component is selected from the group consisting of 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.

14. The hydrocracking catalyst according to claim 11, wherein the inorganic oxide component includes alumina.

15. The hydrogenocrack catalyst according to claim 14, wherein the crystalline microporous material comprises FAU zeolite.

16. The hydrocracking catalyst according to claim 15, wherein the active metal component comprises one or more of Mo, W, Co, or Ni (oxide or sulfide).

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