Zeolite compositions and methods of synthesizing the same

Abstract

Lta cage containing aluminosilicate zeolite compositions and methods for synthesizing the same are described. The methods include providing an alumina source, a silica source, and a heterocyclic aza-crown ether and mixing the elements to form a synthesizing mixture. The synthesizing mixture is then subjected to crystallization conditions to form an aluminosilicate zeolite composition.

Description

ZEOLITE COMPOSITIONS AND METHODS OF SYNTHESIZING THE SAMEBACKGROUND

[0001] There is an urgent and unaddressed societal imperative of fostering a cleaner environment conducive to a more sustainable society. The detrimental environmental effects of fossil fuel combustion, such as the emissions of carbon dioxide (CO2) and nitrogen oxide (NO;i: N2O, NO and NO2), are significant. CO2 emissions are the primary culprits of anthropogenic global warming, which is responsible for the substantial financial obligation of industrial carbon taxes. In addition, NO.V, another influential greenhouse gas, serves as a key precursor to the production of the fine particulate matter (PM2.5; size of 2.5 nm or below) and ozone.

[0002] Zeolites and zeolite-based materials are one of the promising classes of materials for CO2 capture. The capacity and selectivity for CO2 are controlled by interactions between CO2 and the structures either through ion-quadrupole or acid-base interactions. In this respect, the ability to tune Si / Al ratio of specific zeolite framework structures is valuable to modify both their capacity and selectivity. There exists a need for expanding the achievable Si / Al ratios for Ita cage containing zeolites to tune capacity and selectivity towards CO2 adsorption.

[0003] Zeolites and associated microporous materials have attracted considerable interest in the critical category of industrial catalysts and adsorbents. This trend led to a surge in attention devoted to the discovery of novel small-pore zeolites, resulting in successful formulation of the DeNO.v catalyst Cu-SSZ-13 and MTO catalyst H-SAPO-34. Cu-ion exchanged zeolites containing Ita cages are gaining attention due to the excellent hydrothermal stability and performance of Cu-LTA in NHs-selective catalytic reduction (SCR) compared to their counterparts, Cu-SSZ-13 and Cu-ZSM-5. Notably, the Cu2+cations positioned at the center of the single 6-membered ring of the Ita cage exhibit strong catalytic activity while concurrently offering protection against dealumination during the hydrothermal aging process. (Ryu, Taekyung. et al. Fully Copper-Exchanged High-Silica LTA Zeolites as Unrivaled Hydrothermally Stable NH3-SCR Catalysts. Angew. Chem. Int. Ed. 2017, 56. 3256).

[0004] Additionally, increasing Si / Al ratios can improve hydrothermal stability and unlock numerous practical applications for zeolites. RHO zeolites with a Si / Al ratio of 8.0 have been synthesized using 18-crown-6, sodium, cesium cations in fluoride media. (Ahn, N. H. et al. The origin of an unexpected increase in NH3-SCR activity of aged Cu-LTA catalysts. ACS Catal 7, 6781-6785 (2017)). Additionally, RHO zeolites without the use of a fluoride media1ACTIVE\ 1627190097.1have been produced with a SAR of 3.5. (Lozinska, M. M. et al. Understanding carbon dioxide adsorption on univalent cation forms of the flexible zeolite Rho at conditions relevant to carbon capture from flue gases. J Am Chem Soc 134, 17628-17642 (2012)). UFI zeolites with a Si / Al ratio of 11.0 have been synthesized using the l,2-dimethyl-3-(2-fluorobenzyl)imidazolium (12DM3(2FB)I) as structure directing agent with TMA+cation and F’ anion. (Jo, D. et al. Synthesis of High-Silica LTA and UFI Zeolites and NH3-SCR Performance of Their Copper- Exchanged Form. ACS Catal 6, 2443-2447 (2016)). LTA zeolites with Si / Al ratio of 8.3 have been synthesized using l,2-dimethyl-3-(4-methylbeznly)imidazolium and tetramethylammonium ions as organic structure-directing agents (OSD As) in fluoride media, while LTA zeolites with Si / Al ratio of 5.5 have bee produced without the use of a fluoride media. (Jo, D. et al. Synthesis of High-Silica LTA and UFI Zeolites and NH3-SCR Performance of Their Copper-Exchanged Form. ACS Catal 6, 2443-2447 (2016)). KFI-type zeolite have additionally been considered as an environmental catalyst because of its pore size (3.9 A) and sizable cavities. Previous versions of KFI aluminosilicate zeolites have not had a Si / Al ratio greater than 5. (Han, S. C.; Tang, X. M.; Wang, L. J.; Ma, Y. H.; Chen, W.; Wu, Q. M.; Zhang, L.; Zhu, Q. Y.; Meng, X. J.; Zheng, A. M.; Xiao, and F. S. Potassium-directed Sustainable Synthesis of New High Silica Small-Pore Zeolite with KFI Structure (ZJM-7) as an Efficient Catalyst for NH3-SCR Reaction, AppL Catal. B Environ. , 2021, 281, 119480).

[0005] For NH3 SCR catalysts, in addition to having high NOx reduction capability, reduced N2O byproduct formation and higher stability against sulfur species formed during fuel combustion are some of the desired aspects for fulfilling environmental regulations and to mitigate pollution for a sustainable society. There is a need for improvements in the synthesis of zeolite compositions with improved deNOx and N2O formulation capabilities and CO2 adsorbent capabilities.SUMMARY

[0006] In some aspects, the techniques described herein relate to a method of synthesizing an Ita cage containing aluminosilicate zeolite composition, the method including: providing an alumina source, a silica source, and an organic structure directing agent including a heterocyclic aza-crown ether; mixing the alumina source, silica source, and organic structure directing agent to create a synthesizing mixture; and subjecting the synthesizing mixture to crystallization conditions to form an aluminosilicate zeolite, wherein the Ita cage containing aluminosilicate zeolite composition has a molar ratio of silica-to-alumina (SAR) of the composition greater than about 8.2ACTIVE\ 1627190097.1

[0007] In some aspects, the techniques described herein relate to a method, wherein the Ita cage containing aluminosilicate zeolite composition includes one of an RHO zeolite, KFI zeolite, LTA zeolite, or UFI zeolite.

[0008] In some aspects, the techniques described herein relate to a method, wherein the heterocyclic aza-crown ether is 4,7,13,16,21,24-Hexaoxa-l,10-diazabicyclo[8.8.8]hexacosane.

[0009] In some aspects, the techniques described herein relate to a method, further including: providing at least one cation source; and mixing the at least one cation source into the synthesizing mixture, wherein the at least one cation source includes one or more of tetramethylammonium, sodium, cesium, potassium, and strontium.

[0010] In some aspects, the techniques described herein relate to a method, wherein the Ita cage containing aluminosilicate zeolite composition includes an RHO zeolite with a SAR of greater than about 8 and wherein the composition is substantially free of fluoride.

[0011] In some aspects, the techniques described herein relate to a method, wherein the Ita cage containing aluminosilicate zeolite composition includes a UFI zeolite with a SAR of greater than about 14 and wherein the composition is substantially free of fluoride.

[0012] In some aspects, the techniques described herein relate to a method, wherein the Ita cage containing aluminosilicate zeolite composition includes a KFI zeolite with a SAR of greater than about 10.5.

[0013] In some aspects, the techniques described herein relate to a method, wherein the Ita cage containing aluminosilicate zeolite composition includes an LTA zeolite with a SAR of greater than about 14 and wherein the composition is substantially free of fluoride.

[0014] In some aspects, the techniques described herein relate to a method, wherein the Ita cage containing aluminosilicate zeolite composition includes a KFI zeolite and wherein the KFI zeolite has a unit cell volume less than about 6500 A3.

[0015] In some aspects, the techniques described herein relate to a method, wherein the Ita cage containing aluminosilicate zeolite composition includes a KFI zeolite and wherein the KFI zeolite has a unit cell volume less than about 6480 A3.

[0016] In some aspects, the techniques described herein relate to a method, wherein the Ita cage containing aluminosilicate zeolite composition includes an RHO zeolite and wherein the RHO zeolite has a unit cell volume of less than about 3325 A3.

[0017] In some aspects, the techniques described herein relate to a method, wherein the Ita cage containing aluminosilicate zeolite composition includes an RHO zeolite and wherein the RHO zeolite has a unit cell volume of less than about 3320 A3.3ACTIVE\ 1627190097.1

[0018] In some aspects, the techniques described herein relate to a method, wherein the Ita cage containing aluminosilicate zeolite composition includes a UFI zeolite and wherein the UFI zeolite has a unit cell volume less than about 4200 A3.

[0019] In some aspects, the techniques described herein relate to a method, wherein the Ita cage containing aluminosilicate zeolite composition includes a UFI zeolite and wherein the UFI zeolite has a unit cell volume less than about 4190 A3.

[0020] In some aspects, the techniques described herein relate to an Ita cage containing aluminosilicate zeolite composition including: a molar ratio of silica-to-alumina (SAR) of the composition greater than about 8; wherein the Ita cage containing aluminosilicate zeolite composition is synthesized by; providing an alumina source, a silica source, and an organic structure directing agent including a heterocyclic aza-crown ether; mixing the alumina source, silica source, and organic structure directing agent to create a synthesizing mixture; and subjecting the synthesizing mixture to crystallization conditions to form an aluminosilicate zeolite.

[0021] In some aspects, the techniques described herein relate to a Ita cage containing aluminosilicate zeolite composition, wherein the organic structure directing agent includes 4,7,13,16,21 ,24-Hexaoxa- 1 , 10-diazabicyclo[8.8.8]hexacosane.

[0022] In some aspects, the techniques described herein relate to a Ita cage containing aluminosilicate zeolite composition, wherein the Ita cagecontaining aluminosilicate zeolite composition includes one of an RHO zeolite, KFI zeolite, LTA zeolite, or UFI zeolite.

[0023] In some aspects, the techniques described herein relate to a Ita cage containing aluminosilicate zeolite composition, wherein the Ita cage containing aluminosilicate zeolite composition includes an RHO zeolite with a SAR of greater than about 8 and wherein the composition is substantially free of fluoride.

[0024] In some aspects, the techniques described herein relate to a Ita cage containing aluminosilicate zeolite composition, wherein the Ita cage containing aluminosilicate zeolite composition includes a UFI zeolite with a SAR of greater than about 14 and wherein the composition is substantially free of fluoride.

[0025] In some aspects, the techniques described herein relate to a Ita cage containing aluminosilicate zeolite composition, wherein the Ita cage containing aluminosilicate zeolite composition includes an LTA zeolite with a SAR of greater than about 14 and wherein the composition is substantially free of fluoride.4ACTIVE\ 1627190097.1

[0026] In some aspects, the techniques described herein relate to a Ita cage containing aluminosilicate zeolite composition, wherein the Ita cage containing aluminosilicate zeolite composition includes an KFI zeolite with a SAR of greater than about 10.5.

[0027] In some aspects, the techniques described herein relate to a Ita cage containing aluminosilicate zeolite composition including a KFI zeolite with a unit cell volume less than about 6500 A3.

[0028] In some aspects, the techniques described herein relate to a Ita cage containing aluminosilicate zeolite composition including an RHO zeolite with a unit cell volume of less than about 3325 A3.

[0029] In some aspects, the techniques described herein relate to a Ita cage containing aluminosilicate zeolite composition including a UFI zeolite with a unit cell volume less than about 4200 A3.

[0030] In some aspects, the techniques described herein relate to an Ita cage containing aluminosilicate zeolite precursor composite including: a molar ratio of silica-to-alumina (SAR) of the composition greater than about 8; and a plurality of unit cells, wherein each of the plurality of unit cells includes: an Ita cage; and an amount of an organic structure directing agent positioned within the Ita cage.

[0031] In some aspects, the techniques described herein relate to a Ita cage containing aluminosilicate zeolite precursor composite, wherein the organic structure directing agent includes a heterocyclic aza-crown ether.

[0032] In some aspects, the techniques described herein relate to a Ita cage containing aluminosilicate zeolite precursor composite, wherein the organic structure directing agent includes 4,7,13,16,21 ,24-Hexaoxa- 1 , 10-diazabicyclo[8.8.8]hexacosane.

[0033] In some aspects, the techniques described herein relate to a Ita cage containing aluminosilicate zeolite precursor composite, wherein the containing aluminosilicate zeolite composition includes one of an RHO zeolite, KFI zeolite, LTA zeolite, or UFI zeolite.

[0034] In some aspects, the techniques described herein relate to a Ita cage containing aluminosilicate zeolite precursor composite, wherein the Ita cage containing aluminosilicate zeolite composition is substantially free of fluoride.

[0035] In some aspects, the techniques described herein relate to a Ita cage containing aluminosilicate zeolite precursor composite, wherein the Ita cage containing aluminosilicate zeolite composition includes an RHO zeolite with a SAR of greater than about 8 and wherein the composition is substantially free of fluoride.5ACTIVE\ 1627190097.1

[0036] In some aspects, the techniques described herein relate to a Ita cage containing aluminosilicate zeolite precursor composite, wherein the Ita cage containing aluminosilicate zeolite composition includes a UFI zeolite with a SAR of greater than about 14 and wherein the composition is substantially free of fluoride.

[0037] In some aspects, the techniques described herein relate to a Ita cage containing aluminosilicate zeolite precursor composite, wherein the Ita cage containing aluminosilicate zeolite composition includes an LTA zeolite with a SAR of greater than about 14 and wherein the composition is substantially free of fluoride.

[0038] In some aspects, the techniques described herein relate to a Ita cage containing aluminosilicate zeolite precursor composite, wherein the Ita cage containing aluminosilicate zeolite composition includes an KFI zeolite with a SAR of greater than about 10.5.

[0039] In some aspects, the techniques described herein relate to an adsorbent material effective for the removal 15 to 24.

[0040] In some aspects, the techniques described herein relate to a method 15 to 24; and contacting the Ita cage containing aluminosilicate zeolite composition with the gaseous stream including CO2.

[0041] In some aspects, the techniques described herein relate to a method, wherein the gaseous stream includes one of industrial flue gas, HVAC air streams, or an air stream for the direct air capture of CO2.

[0042] In some aspects, the techniques described herein relate to a selective catalytic reduction (SCR) catalyst effective for the abatement 15 to 24, wherein the Ita cage containing aluminosilicate zeolite composition includes a promoter material.

[0043] In some aspects, the techniques described herein relate to a SCR catalyst, wherein the promoter metal is present in an amount of about 1.0 wt. % to about 10 wt. %, based on the total weight of the SCR catalyst, and calculated as the metal oxide.

[0044] In some aspects, the techniques described herein relate to a SCR catalyst, wherein the promoter metal is present in an amount of about 3 wt. % to about 6 wt. %.

[0045] In some aspects, the techniques described herein relate to a SCR catalyst, wherein the promoter metal is selected from iron, copper, and combinations thereof.

[0046] In some aspects, the techniques described herein relate to a method 37 to 40; and contacting the SCR catalyst with a combustion engine exhaust stream wherein the combustion engine exhaust stream includes NOx.6ACTIVE\ 1627190097.1BRIEF DESCRIPTION OF DRAWINGS

[0047] FIG. 1 depicts a flow diagram of a method of manufacturing a Ita cage containing aluminosilicate zeolite composition in accordance with embodiments of the disclosure.

[0048] FIG. 2A depicts an illustrative diagram of an RHO zeolite structure in accordance with embodiments of the disclosure.

[0049] FIG. 2B depicts an illustrative diagram of RHO zeolite components in accordance with embodiments of the disclosure.

[0050] FIG. 3 A depicts an illustrative diagram of an LTA zeolite structure in accordance with embodiments of the disclosure.

[0051] FIG. 3B depicts an illustrative diagram of LTA zeolite components in accordance with embodiments of the disclosure.

[0052] FIG. 4A depicts an illustrative diagram of a UFI zeolite structure in accordance with embodiments of the disclosure.

[0053] FIG. 4B depicts an illustrative diagram of UFI zeolite components in accordance with embodiments of the disclosure.

[0054] FIG. 5A depicts an illustrative diagram of a KFI zeolite structure in accordance with embodiments of the disclosure.

[0055] FIG. 5B depicts an illustrative diagram of KFI zeolite components in accordance with embodiments of the disclosure.

[0056] FIG. 6 depicts an illustrative diagram of an Ita cage containing an organic structure directing agent in accordance with embodiments of the disclosure.

[0057] FIGS. 7-18 each depict a graphical representation of the structure of a synthesized Ita cage containing aluminosilicate zeolite composition in accordance with several embodiments of the disclosure.DEFINITIONS

[0058] As used herein, the term “about” when immediately preceding a numerical value means a range of plus or minus 10% of that value, for example, “about 50” means 45 to 55, “about 25,000” means 22,500 to 27,500, etc., unless the context of the disclosure indicates otherwise, or is inconsistent with such an interpretation.

[0059] As used herein, the term “heterocyclic aza-crown ether” refers to a cyclic aza analog of a crown ether. For example, a heterocyclic aza-crown ether may comprise 4,7,13,16,21,24- Hexaoxa-l,10-diazabicyclo[8.8.8]hexacosane.

[0060] The present disclosure is not to be limited in terms of the particular embodiments described in this application, which are intended as illustrations of various aspects. Many7ACTIVE\ 1627190097.1modifications and variations can be made without departing from its spirit and scope, as will be apparent to those skilled in the art. Functionally equivalent methods and apparatuses within the scope of the disclosure, in addition to those enumerated herein, will be apparent to those skilled in the art from the descriptions. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that this disclosure is not limited to particular methods, reagents, compounds, compositions or biological systems, which can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0061] As used in this document, the singular forms “a,” “an,” and “the” include plural references unless the context clearly dictates otherwise. Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art. Nothing in this disclosure is to be construed as an admission that the embodiments described in this disclosure are not entitled to antedate such disclosure by virtue of prior invention. As used in this document, the term “comprising” means “including, but not limited to.”

[0062] As used herein, the term “silica-to-alumina ratio (SAR)” refers to the molar ratio of SiC>2 to AI2O3 present in a zeolite composition. For example, a zeolite composition may comprise an SAR of about 14.

[0063] As used herein, the term “Si / Al ratio” refers to the molar ratio of silicon to aluminum present in a zeolite composition. For example, a zeolite composition may comprise an Si / Al ratio of about 7.

[0064] While various compositions, methods, and devices are described in terms of "comprising" various components or steps (interpreted as meaning "including, but not limited to"), the compositions, methods, and devices can also "consist essentially of' or "consist of' the various components and steps, and such terminology should be interpreted as defining essentially closed-member groups.

[0065] With respect to the use of substantially any plural and / or singular terms herein, those having skill in the art can translate from the plural to the singular and / or from the singular to the plural as is appropriate to the context and / or application. The various singular / plural permutations may be expressly set forth herein for sake of clarity.

[0066] It will be understood by those within the art that, in general, terms used herein, and especially in the appended claims (for example, bodies of the appended claims) are generally8ACTIVE\ 1627190097.1intended as “open” terms (for example, the term “including” should be interpreted as “including but not limited to,” the term “having” should be interpreted as “having at least,” the term “includes” should be interpreted as “includes but is not limited to,” etc.). It will be further understood by those skilled in the art that if a specific number of an introduced claim recitation is intended, such an intent will be explicitly recited in the claim, and in the absence of such recitation no such intent is present. For example, as an aid to understanding, the following appended claims may contain usage of the introductory phrases "at least one" and "one or more" to introduce claim recitations. However, the use of such phrases should not be construed to imply that the introduction of a claim recitation by the indefinite articles "a" or "an" limits any particular claim containing such introduced claim recitation to embodiments containing only one such recitation, even when the same claim includes the introductory phrases "one or more" or "at least one" and indefinite articles such as "a" or "an" (for example, “a” and / or “an” should be interpreted to mean “at least one” or “one or more”); the same holds true for the use of definite articles used to introduce claim recitations. In addition, even if a specific number of an introduced claim recitation is explicitly recited, those skilled in the art will recognize that such recitation should be interpreted to mean at least the recited number (for example, the bare recitation of "two recitations," without other modifiers, means at least two recitations, or two or more recitations). Furthermore, in those instances where a convention analogous to “at least one of A, B, and C, etc.” is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (for example, “ a system having at least one of A, B, and C” would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and / or A, B, and C together, etc.). In those instances where a convention analogous to “at least one of A, B, or C, etc.” is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (for example, “ a system having at least one of A, B, or C” would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and / or A, B, and C together, etc.). It will be further understood by those within the art that virtually any disjunctive word and / or phrase presenting two or more alternative terms, whether in the description, claims, or drawings, should be understood to contemplate the possibilities of including one of the terms, either of the terms, or both terms. For example, the phrase “A or B” will be understood to include the possibilities of “A” or “B” or “A and B.”9ACTIVE\ 1627190097.1

[0067] In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.

[0068] As will be understood by one skilled in the art, for any and all purposes, such as in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc. As will also be understood by one skilled in the art all language such as “up to,” “at least,” and the like include the number recited and refer to ranges which can be subsequently broken down into subranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member. Thus, for example, a group having 1-3 cells refers to groups having 1, 2, or 3 compounds. Similarly, a group having 1-5 compounds refers to groups having 1, 2, 3, 4, or 5 compounds, and so forth.DETAILED DESCRIPTION

[0069] This disclosure is not limited to the particular systems, devices and methods described, as these may vary. The terminology used in the description is for the purpose of describing the particular versions or embodiments only and is not intended to limit the scope.

[0070] Methods

[0071] Methods can be assembled for the synthesis of zeolite compositions. The methods comprise providing an alumina source, a silica source, and an organic structure directing agent. In some embodiments, the organic structure directing agent is a heterocyclic aza-crown ether. The method further comprises mixing the alumina source, silica source, and organic structure directing agent to create a synthesizing mixture and subjecting the synthesizing mixture to crystallization conditions to form an aluminosilicate zeolite composition. The use of the heterocyclic aza-crown ether enables the synthesis of zeolite compositions with higher molar ratio of silica-to-alumina than zeolite compositions synthesized without a heterocyclic aza- crown ether.

[0072] FIG. 1 depicts a flow diagram of a method of synthesizing an Ita cage containing aluminosilicate zeolite composition. The method comprises providing 101 an alumina source, a silica source, and an organic structure directing agent. In some embodiments, the alumina source is one of aluminum powder, aluminum hydroxide, or types of alumina phases such as boehmite, pseudoboehmite, gamma alumina, aluminum triisopropoxide, aluminum sec-10ACTIVE\ 1627190097.1butoxide, an aluminum salt, alkali aluminates, colloidal alumina, or a zeolite. In some embodiments, the silica source is colloidal silica, fumed silica, precipitated silica, a mineral or synthetic amorphous aluminosilicate, clays, zeolites or dissolved silicas such as sodium silicate. The organic structure directing agent may be any material effective for directing the formation of the zeolite structures known to one of skill in the art. In some embodiments, the organic structure directing agent comprises a heterocyclic aza-crown ether. In some embodiments, the heterocyclic aza-crown ether comprises 4,7,13,16,21,24-Hexaoxa-l,10- diazabicyclo[8.8.8]hexacosane.

[0073] The method further comprises mixing 102 the alumina source, the silica source, and the organic structure directing agent to create a synthesizing mixture. The synthesizing mixture may comprise any molar ratio of alumina to the organic structure directing agent effective for the synthesis of zeolite compositions. In some embodiments, the synthesizing mixture has a molar ratio of alumina to the organic structure directing agent of about 20: 1, about 19:1, about 18:1, about 17:1, about 16:1, about 15:1, about 14:1, about 13:1, about 12:1, about 11:1, about 10:1, about 9:1, about 8:1, about 7:1, about 6:1, about 5:1, about 4:1, about 3:1, about 2:1, about 1:1, about 1:2, about 1:3, about 1:4, about 1:5, about 1:6, about 1:7, about 1:8, about 1:9, about 1:10, about 1:11, about 1:12, about 1:13, about 1:14, about 1:15, about 1:16, about 1:17, about 1:18, about 1:19, about 1:20, or any value or range of values between any two of these values.

[0074] The synthesizing mixture may comprise any molar ratio of silica to alumina effective for the synthesis of zeolite compositions. In some embodiments, the synthesizing mixture has a molar ratio of silica to alumina of about 100:1, about 95:1, about 90:1, about 85:1, about 80:1, about 75:1, about 70:1, about 65:1, about 60:1, about 55:1, about 50:1, about 45:1, about 40:1, about 35:1, about 30:1, about 25:1, about 20:1, about 19:1, about 18:1, about 17:1, about 16:1, about 15:1, about 14:1, about 13:1, about 12:1, about 11:1, about 10:1, about 9:1, about 8:1, about 7:1, about 6:1, about 5:1, about 4:1, about 3:1, about 2:1, about 1 : 1 , or any value or range of values between any two of these values.

[0075] The method further comprises subjecting 103 the synthesizing mixture to crystallization conditions to form an aluminosilicate zeolite. In some embodiments, subjecting 103 the synthesizing mixture to crystallization conditions to form an aluminosilicate zeolite comprises stirring the synthesizing solution and heating the synthesizing solution. In some embodiments, the synthesizing solution is stirred at room temperature. In some embodiments, the synthesizing solution is stirred for about 0 hours, about 1 hour, about 2 hours, about 3 hours, about 4 hours, about 5 hours, about 6 hours, about 7 hours, about 8 hours, about 9 hours, about 10 hours, about 11ACTIVE\ 1627190097.111 hours, about 12 hours, about 13 hours, about 14 hours, about 15 hours, about 16 hours, about 17 hours, about 18 hours, about 19 hours, about 20, hours, about 21 hours, about 22 hours, about 23 hours, about 24 hours, about 25 hours, about 26 hours, about 27 hours, about 28 hours, about 29 hours, about 30 hours, or any value or range of values between any two of these values.

[0076] The synthesizing solution may be heated to any temperature effective for the synthesis of zeolite compositions. In some embodiments, the synthesizing solution is heated to a temperature of about 100 °C, about 105 °C, about 110 °C, about 115 °C, about 120 °C, about 125 °C, about 130 °C, about 135 °C, about 140 °C, about 145 °C, about 150 °C, about 155 °C, about 160 °C, about 165 °C, about 170 °C, about 175 °C, about 180 °C, about 185 °C, about 190 °C, about 195 °C, about 200 °C, or any value or range of values between any two of these values. In some embodiments, the synthesizing solution is heated for about 0 hours, about 12 hours, about 24 hours, about 36 hours, about 48 hours, about 60 hours, about 72 hours, about 84 hours, about 96 hours, about 108 hours 120 hours, about 132 hours, about 144 hours, about 156 hours, about 168 hours, about 180 hours, about 192 hours, 204 hours, about 216 hours, about 228 hours, about 240 hours, about 252 hours, about 264 hours, about 276 hours, about 288 hours, about 300 hours, about 324, about 336 hours, or any value or range of values between any two of these values. In some embodiments, the synthesizing solution is heated for about 0 hours to about 336 hours.

[0077] In some embodiments, the method further comprises filtering the heated mixture to recover the solid zeolite composition. In some embodiments, filtering the heated mixture comprises one or more of filtration or centrifugation. In some embodiments, the method further comprises washing the filtered mixture with deionized water. In some embodiments, the method further comprises calcining the mixture. The mixture may be calcined at any temperature effective for the removal of the structures directing agents. In some embodiments, the mixture is calcined at a temperature of about 450 °C, about 460 °C, about 470 °C, about 480 °C, about 490 °C, about 500 °C, about 510 °C, about 520 °C, about 530 °C, about 540 °C, about 550 °C, about 560 °C, about 570 °C, about 580 °C, about 590 °C, about 600 °C, 610 °C, about 620 °C, about 630 °C, about 640 °C, about 650 °C, 660 °C, about 670 °C, about 680 °C, about 690 °C, about 700 °C, or any value or range of values between any two of these values. In some embodiments, the mixture is calcined for about 0.5 hours, about 1 hour, about 1.5 hours, about 2 hours, about 2.5 hours, about 3 hours, about 3.5 hours, about 4 hours, about 4.5 hours, about 5 hours, about 5.5 hours, about 6 hours, about 6.5 hours, about 7 hours, about 7.5 hours, about 8 hours, or any value or range of values between any two of these values.12ACTIVE\ 1627190097.1

[0078] In some embodiments, the method further comprises providing at least one cation source and mixing the at least one cation source into the synthesizing mixture. The cation source may comprise any material effective for the synthesis of zeolite compositions known to one of skill in the art. In some embodiments, the cation source comprises one or more of tetramethylammonium, sodium, cesium, potassium, and strontium. In some embodiments, the cation source comprises one or more of tetramethylammonium hydroxide pentahydrate (TMAOH 5H2O), alkali metal hydroxides such as potassium hydroxide (KOH), cesium hydrate (CsOH) or sodium hydroxide (NaOH), an alkali metal salt, an alkaline earth metal salt such as strontium nitrate (SrfNOsh), an alkaline earth metal hydroxide, or a quaternary ammonium cation with the form NR1R2R3R4, wherein each of Ri, R2, FC.and R4 is one of an alkyl group, an aryl group, or an organyl group.

[0079] The synthesizing mixture may comprise any molar ratio of alumina to the cation source effective for the synthesis of zeolite compositions. In some embodiments, the synthesizing mixture has a molar ratio of alumina to the cation source of about 10: 1, about 9: 1, about 8: 1, about 7: 1, about 6: 1, about 5: 1, about 4: 1, about 3 : 1, about 2: 1, about 1 : 1, about 1 :2, about 1 :3, about 1 :4, about 1 :5, about 1 :6, about 1 :7, about 1 :8, about 1 :9, about 1 : 10, or any value or range of values between any two of these values.

[0080] In some embodiments, the method further comprises providing a target material crystal and mixing the target material crystal seed into the synthesizing mixture. In some embodiments, the target material crystal seed is configured to accelerate the crystallization kinetics of the synthesizing mixture. In some embodiments, the target material crystal seed comprises a KFI seed, a UFI seed, an LTA seed, or an RHO seed. In some embodiments, the target material crystal seed is provided in a proton form. The target material crystal seed may be provided in any amount effective for the synthesis of zeolite compositions. In some embodiments, the target zeolite crystal seed is provided in an amount with respect to the mass of the silica in the synthesizing mixture of about 0.1 wt. %, about 0.2 wt. %, about 0.3 wt. %, about 0.4 wt. %, about 0.5 wt. %, about 0.6 wt. %, about 0.7 wt. %, about 0.8 wt. %, about 0.9 wt. %, about 1 wt. %, about 2 wt. %, about 3 wt. %, about 4 wt. %, about 5 wt. %, about 6 wt. %, about 7 wt. %, about 8 wt. %, or any value range of values between any two of these values.

[0081] In some embodiments, the method comprises providing CuO and mixing the CuO into the synthesizing mixture. The CuO may be provided in any amount effective for the removal of nitrous oxide from a gaseous stream. In some embodiments, the CuO is provided in an amount with respect to the total mass of the synthesizing mixture of about 0. 1 wt. %, about 0.2 wt. %, about 0.3 wt. %, about 0.4 wt. %, about 0.5 wt. %, about 0.6 wt. %, about 0.7 wt. %,13ACTIVE\ 1627190097.1about 0.8 wt. %, about 0.9 wt. %, about 1 wt. %, 1.1 wt. %, about 1.2 wt. %, about 1.3 wt. %, about 1.4 wt. %, about 1.5 wt. %, about 1.6 wt. %, about 1.7 wt. %, about 1.8 wt. %, about 1.9 wt. %, about 2.0 wt. %, about 2.1 wt. %, about 2.2 wt. %, about 2.3 wt. %, about 2.4 wt. %, about 2.5 wt. %, about 2.6 wt. %, about 2.7 wt. %, about 2.8 wt. %, about 2.9 wt. %, about 3.0 wt. %, about 3.1 wt. %, about 3.2 wt. %, about 3.3 wt. %, about 3.4 wt. %, about 3.5 wt. %, about 3.6 wt. %, about 3.7 wt. %, about 3.8 wt. %, about 3.9 wt. %, about 4.0 wt. %, about 4.1 wt. %, about 4.2 wt. %, about 4.3 wt. %, about 4.4 wt. %, about 4.5 wt. %, about 4.6 wt. %, about 4.7 wt. %, about 4.8 wt. %, about 4.9 wt. %, about 5.0 wt. %, or any value range of values between any two of these values.

[0082] In some embodiments, the method further comprises providing H2O and mixing the H2O into the synthesizing mixture. The synthesizing mixture may comprise any molar ratio of H2O to silica effective for the synthesis of zeolite compositions. In some embodiments, the synthesizing mixture has a molar ratio of H2O to silica of about 300:1, about 295:1, about 290:1, about 285:1, about 280:1, about 275:1, about 270:1, about 265:1, about 260:1, about255:1, about 250:1, about 245:1, about 240:1, about 235:1, about 230:1, about 225:1, about220:1, about 215:1, about 210:1, about 205:1, about 200:1, about 195:1, about 190:1, about185:1, about 180:1, about 175:1, about 170:1, about 165:1, about 160:1, about 155:1, about150:1, about 145:1, about 140:1, about 135:1, about 130:1, about 115:1, about 120:1, about125:1, about 110:1, about 105:1, about 100:1, about 95:1, about 90:1, about 85:1, about 80:1, about 75:1, about 70:1, about 65:1, about 60:1, about 55:1, about 50:1, about 45:1, about 40:1, about 35:1, about 30:1, about 25:1 about 24:1, about 23:1, about 22:1, about 21:1, about 20:1, about 19:1, about 18:1, about 17:1, about 16:1, about 15:1, about 14:1, about 13:1, about 12:1, about 11:1, about 10:1, about 9:1, about 8:1, about 7:1, about 6:1, about 5:1, or any value or range of values between any two of these values.

[0083] Compositions

[0084] Zeolite compositions may be synthesized using the above-described methods. In some embodiments, the zeolite compositions comprise an Ita cage containing aluminosilicate zeolite composition. In some embodiments, the Ita cage containing aluminosilicate zeolite compositions comprise one of an RHO zeolite, an LTA zeolite, a UFI zeolite, or a KFI zeolite as determined by the International Zeolite Association (IZA)-Structure Commission database.

[0085] FIGS. 2 A and B depict illustrative diagrams of an RHO zeolite structure. The RHO zeolite structure comprises a plurality of Ita cages 201 and d8r units 202. The RHO zeolite may comprise any SAR value effective for the removal of nitrous oxide from a gaseous stream. In some embodiments, the RHO zeolite has a SAR ratio of greater than about 17.0, about 17.1, 14ACTIVE\ 1627190097.1about 17.2, about 17.3, about 17.4, about 17.5, about 17.6, about 17.7, about 17.8, about 17.9, about 18.0, about 18.1, about 18.2, about 18.3, about 18.4, about 18.5, about 18.6, about 18.7, about 18.8, about 18.9, about 19.0, about 19.1, about 19.2, about 19.3, about 19.4, about 19.5, about 19.6, about 19.7, about 19.8, about 19.9, about 20.0, or any value range of values between any two of these values. In some embodiments, the RHO zeolite has an SAR ratio of about 17.0 to about 40.0, about 17.5 to about 30.0, or about 18.0 to about 20.0.

[0086] In some embodiments, the RHO zeolite structure does not comprise fluoride. In such an embodiment, the RHO zeolite may comprise any SAR value effective for the removal of nitrous oxide from a gaseous stream. In such an embodiment, the RHO zeolite may have an SAR ratio of greater than about 8.0, about 8.1, about 8.2, about 8.3, about 8.4, about 8.5, about 8.6, about 8.7, about 8.8, about 8.9, about 9.0, about 9.1, about 9.2, about 9.3, about 9.4, about 9.5, about 9.6, about 9.7, about 9.8, about 9.9, about 10.0, about 10.1, about 10.2, about 10.3, about 10.4, about 10.5, about 10.6, about 10.7, about 10.8, about 10.9, about 11.0, about 11.1, about 11.2, about 11.3, about 11.4, about 11.5, about 11.6, about 11.7, about 11.8, about 11.9, about 12.0, about 12.1, about 12.2, about 12.3, about 12.4, about 12.5, about 12.6, about 12.7, about 12.8, about 12.9, about 13.0, or any value range of values between any two of these values. In such an embodiment, the RHO zeolite may have an SAR ratio of about 10.0 to about 40.0, about 10.0 to 20.0, about 10.5 to about 30.0, or about 11.0 to about 20.0.

[0087] The RHO zeolite may comprise any unit cell volume effective for the removal of nitrous oxide from a gaseous stream. In some embodiments, the RHO zeolite has a unit cell volume of less than about 3330 A3, about 3329 A3, about 3328 A3, about 3327 A3, about 3326 A3, about3325 A3, about 3324 A3, about 3323 A3, about 3322 A3, about 3321 A3, about 3320 A3, about3319 A3, about 3318 A3, about 3317 A3, about 3316 A3, about 3315 A3, about 3314 A3, about3313 A3, about 3312 A3, about 3311 A3, about 3310 A3, about 3309 A3, about 3308 A3, about3307 A3, about 3306 A3, about 3305 A3, about 3304 A3, about 3303 A3, about 3302 A3, about3301 A3, about 3300 A3, about 3299 A3, about 3298 A3, about 3297 A3, about 3296 A3, about3295 A3, about 3294 A3, about 3293 A3, about 3292 A3, about 3291 A3, about 3290 A3, about3289 A3, about 3288 A3, about 3287 A3, about 3286 A3, about 3285 A3, or any value range of values between any two of these values.

[0088] FIGS. 3A and B depict illustrative diagrams of an LTA zeolite structure. The LTA zeolite structure comprises a plurality of Ita cages 301, sod units 302, and d4r units 303. In some embodiments, the LTA zeolite does not comprise fluoride. The LTA zeolite may comprise any SAR value effective for the removal of nitrous oxide from a gaseous stream. In some embodiments, the LTA zeolite has a SAR ratio of greater than about 13.0, about 13.1 15ACTIVE\ 1627190097.1about 13.2, about 13.3 about 13.4, about 13.5, about 13.6, about 13.7, about 13.8, about 13.9, about 14.0, about 14.1, about 14.2, about 14.3, about 14.4, about 14.5, about 14.6, about 14.7, about 14.8, about 14.9, about 15.0, about 15.1, about 15.2, about 15.3, about 15.4, about 15.5, about 15.6, about 15.7, about 15.8, about 15.9, about 16.0, about 16.1, about 16.2, about 16.3, about 16.4, about 16.5, about 16.6, about 16.7, about 16.8, about 16.9, about 17.0, or any value range of values between any two of these values. In some embodiments, the LTA zeolite has an SAR ratio of about 13.0 to about 40.0, about 14.5 to about 30.0, or about 15.0 to about 20.0.

[0089] FIGS. 4 A and B depict illustrative diagrams of an UFI zeolite structure. The UFI zeolite structure comprises a plurality of Ita cages 401, ufi units 402, d4r units 403, and rth units 404. The UFI zeolite may comprise any SAR value effective for the removal of nitrous oxide from a gaseous stream. In some embodiments, the UFI zeolite has a SAR ratio of greater than about 22.0, about 22.1, about 22.2, about 22.3, about 22.4, about 22.5, about 22.6, about 22.7, about22.8, about 22.9, about 23.0, about 23.1, about 23.2, about 23.3, about 23.4, about 23.5, about23.6, about 23.7, about 23.8, about 23.9, about 24.0, about 24.1, about 24.2, about 24.3, about24.4, about 24.5, about 24.6, about 24.7, about 24.8, about 24.9, about 25.0, or any value range of values between any two of these values. In some embodiments, the UFI zeolite has an SAR ratio of about 22.0 to about 40.0, about 22.5 to about 30.0, or about 23.0 to about 25.0.

[0090] In some embodiments, the UFI zeolite structure does not comprise fluoride. In such an embodiment, the UFI zeolite may comprise any SAR value effective for the removal of nitrous oxide from a gaseous stream. In such an embodiment, the UFI zeolite may have an SAR ratio of greater than about 14.0, about 14.1, about 14.2, about 14.3, about 14.4, about 14.5, about14.6, about 14.7, about 14.8, about 14.9, about 15.0, about 15.1, about 15.2, about 15.3, about15.4, about 15.5, about 15.6, about 15.7, about 15.8, about 15.9, about 16.0, about 16.1, about16.2, about 16.3, about 16.4, about 16.5, about 16.6, about 16.7, about 16.8, about 16.9, about17.0, about 18.0, about 18.1, about 18.2, about 18.3, about 18.4, about 18.5, about 18.6, about18.7, about 18.8, about 18.9, about 19.0, about 19.1, about 19.2, about 19.3, about 19.4, about19.5, about 19.6, about 19.7, about 19.8, about 19.9, about 20.0, or any value range of values between any two of these values. In such an embodiment, the UFI zeolite may have an SAR ratio of about 15.0 to about 40.0, about 16.0 to about 30.0, or about 17.0 to about 20.0.

[0091] The UFI zeolite may comprise any unit cell volume effective for the removal of nitrous oxide from a gaseous stream. In some embodiments, the UFI zeolite has a unit cell volume of less than about 4200 A3, about 4199 A3, about 4198 A3, about 4197 A3, about 4196 A3, about4195 A3, about 4194 A3, about 4193 A3, about 4192 A3, about 4191 A3, about 4190 A3, about4189 A3, about 4188 A3, about 4187 A3, about 4186 A3, about 4185 A3, about 4184 A3, about16ACTIVE\ 1627190097.14183 A3, about 4182 A3, about 4181 A3, about 4180 A3, about 4179 A3, about 4178 A3, about4177 A3, about 4176 A3, about 4175 A3, about 4174 A3, about 4173 A3, about 4172 A3, about4171 A3, about 4170 A3, about 4169 A3, about 4168 A3, about 4167 A3, about 4166 A3, about4165 A3, about 4164 A3, about 4163 A3, about 4162 A3, about 4161 A3, about 4160 A3, or any value range of values between any two of these values.

[0092] FIGS. 5 A and B depict illustrative diagrams of an KFI zeolite structure. The KFI zeolite structure comprises a plurality of Ita cages 501, pau units 502, and d6r units 503. The KFI zeolite may comprise any SAR value effective for the removal of nitrous oxide from a gaseous stream. In some embodiments, the KFI zeolite has a SAR ratio of greater than about 10.0, about 10.1, about 10.2, about 10.3, about 10.4, about 10.5, about 10.6, about 10.7, about 10.8, about10.9, about 11.0, about 11.1, about 11.2, about 11.3, about 11.4, about 11.5, about 11.6, about11.7, about 11.8, about 11.9, about 12.0, about 12.1, about 12.2, about 12.3, about 12.4, about12.5, about 12.6, about 12.7, about 12.8, about 12.9, about 13.0, or any value range of values between any two of these values. In some embodiments, the KFI zeolite has an SAR ratio of about 10.0 to about 40.0, about 10.0 to about 30.0, or about 10.0 to about 20.0.

[0093] The KFI zeolite may comprise any unit cell volume effective for the removal of nitrous oxide from a gaseous stream. In some embodiments, the KFI zeolite has a unit cell volume of less than about 6500 A3, about 6495 A3, about 6490 A3, about 6485 A3, about 6480 A3, about6475 A3, about 6470 A3, about 6465 A3, about 6460 A3, about 6455 A3, about 6450 A3, about6445 A3, about 6444 A3, about 6440 A3, about 6435 A3, about 6430 A3, about 6425 A3, about6421 A3, about 6420 A3, about 6415 A3, about 6410 A3, about 6405 A3, about 6400 A3, about6395 A3, about 6390 A3, about 6385 A3, about 6380 A3, about 6375 A3, about 6370 A3, about6365 A3, about 6360 A3, about 6355 A3, about 6350 A3, or any value range of values between any two of these values. In some embodiments, the KFI zeolite has a unit cell volume of about 6421 A3to about 6444 A3.

[0094] In some embodiments, the Ita cage containing aluminosilicate zeolite composition comprises one of Fe20s or CuO. The Fe20s or CuO may be present in the Ita cage containing aluminosilicate zeolite composition in any amount effective for the removal of nitrous oxide from a gaseous stream. In some embodiments, the Fe20s or CuO is present in the Ita cage containing aluminosilicate zeolite composition in an amount with respect to the total mass of the Ita cage containing aluminosilicate zeolite composition of about 3.5 wt. %, about 3.6 wt. %, about 3.7 wt. %, about 3.8 wt. %, about 3.9 wt. %, about 4.0 wt. %, about 4.1 wt. %, about 4.2 wt. %, about 4.3 wt. %, about 4.4 wt. %, about 4.5 wt. %, about 4.6 wt. %, about 4.7 wt. %, about 4.8 wt. %, about 4.9 wt. %, about 5.0 wt. %, about 5.1 wt. %, about 5.2 wt. %, about 17ACTIVE\ 1627190097.15.3 wt. %, about 5.4 wt. %, about 5.5 wt. %, about 5.6 wt. %, about 5.7 wt. %, about 5.8 wt. %, about 5.9 wt. %, about 6.0 wt. %, about 6.1 wt. %, about 6.2 wt. %, about 6.3 wt. %, about6.4 wt. %, about 6.5 wt. %, about 6.6 wt. %, about 6.7 wt. %, about 6.8 wt. %, about 6.9 wt. %, about 7.0 wt. %, about 7.1 wt. %, about 7.2 wt. %, about 7.3 wt. %, about 7.4 wt. %, about7.5 wt. %, about 7.6 wt. %, about 7.7 wt. %, about 7.8 wt. %, about 7.9 wt. %, about 8.0 wt. %, or any value range of values between any two of these values.

[0095] Lta cage containing aluminosilicate zeolite precursor composites may be synthesized using the above-described methods. The lta cage containing aluminosilicate zeolite precursor composite comprises a plurality of lta cages and an amount of an organic structure directing agent positioned within the lta cage. In some embodiments, the lta cage containing aluminosilicate zeolite precursor composite comprises one of an RHO zeolite, an LTA zeolite, a UFI zeolite, or a KFI zeolite. In some embodiments, the RHO zeolite, LTA zeolite, UFI zeolite, or KFI zeolite comprise similar properties as disclosed above.

[0096] FIG. 6 depicts an illustrative diagram of an lta cage 601 with an amount of an organic structure directing agent 602 positioned within the lta cage 601. In some embodiments, the organic structure directing agent comprises a heterocyclic aza-crown ether. In some embodiments, the heterocyclic aza-crown ether comprises 4,7,13,16,21,24-Hexaoxa-l,10- diazabicyclo[8.8.8]hexacosane.

[0097] Methods of Use

[0098] Methods can be assembled to remove nitrous oxide from an exhaust stream using the above-described Ita-cage containing aluminosilicate zeolite compositions.

[0099] A method of removing nitrous oxide from a combustion engine exhaust comprises providing an lta cage containing aluminosilicate zeolite composition. In some embodiments, the lta cage containing aluminosilicate zeolite composition has a SAR greater than about 10.5. In some embodiments, the lta cage containing aluminosilicate zeolite composition has a SAR greater than about 12. In some embodiments, the lta cage containing aluminosilicate zeolite composition comprises one of a KFI zeolite, a UFI zeolite, an RHO zeolite, or an LTA zeolite. The lta cage containing aluminosilicate zeolite composition may contain similar properties as the lta cage containing aluminosilicate zeolite compositions described above.

[0100] In some embodiments, the lta cage containing aluminosilicate zeolite composition comprises a KFI zeolite with a greater than about 10.0, about 10.1, about 10.2, about 10.3, about 10.4, about 10.5, about 10.6, about 10.7, about 10.8, about 10.9, about 11.0, about 11.1, about 11.2, about 11.3, about 11.4, about 11.5, about 11.6, about 11.7, about 11.8, about 11.9, about 12.0, about 12.1, about 12.2, about 12.3, about 12.4, about 12.5, about 12.6, about 12.7,18ACTIVE\ 1627190097.1about 12.8, about 12.9, about 13.0, or any value range of values between any two of these values.

[0101] In some embodiments, the Ita cage containing aluminosilicate zeolite composition comprises a UFI zeolite with a SAR ratio of greater than about 22.0, about 22.1, about 22.2, about 22.3, about 22.4, about 22.5, about 22.6, about 22.7, about 22.8, about 22.9, about 23.0, about 23.1, about 23.2, about 23.3, about 23.4, about 23.5, about 23.6, about 23.7, about 23.8, about 23.9, about 24.0, about 24.1, about 24.2, about 24.3, about 24.4, about 24.5, about 24.6, about 24.7, about 24.8, about 24.9, about 25.0, or any value range of values between any two of these values.

[0102] In some embodiments, the Ita cage containing aluminosilicate zeolite composition comprises a RHO zeolite with an SAR ratio of greater than about 8.0, about 8.1, about 8.2, about 8.3, about 8.4, about 8.5, about 8.6, about 8.7, about 8.8, about 8.9, about 9.0, about 9.1, about 9.2, about 9.3, about 9.4, about 9.5, about 9.6, about 9.7, about 9.8, about 9.9, about 10.0, about 10.1, about 10.2, about 10.3, about 10.4, about 10.5, about 10.6, about 10.7, about 10.8, about 10.9, about 11.0, about 11.1, about 11.2, about 11.3, about 11.4, about 11.5, about 11.6, about 11.7, about 11.8, about 11.9, about 12.0, about 12.1, about 12.2, about 12.3, about 12.4, about 12.5, about 12.6, about 12.7, about 12.8, about 12.9, about 13.0, or any value range of values between any two of these values.

[0103] In some embodiments, the Ita cage containing aluminosilicate zeolite composition comprises an LTA zeolite with an SAR ratio of greater than about 13.0, about 13.1 about 13.2, about 13.3 about 13.4, about 13.5, about 13.6, about 13.7, about 13.8, about 13.9, about 14.0, about 14.1, about 14.2, about 14.3, about 14.4, about 14.5, about 14.6, about 14.7, about 14.8, about 14.9, about 15.0, about 15.1, about 15.2, about 15.3, about 15.4, about 15.5, about 15.6, about 15.7, about 15.8, about 15.9, about 16.0, about 16.1, about 16.2, about 16.3, about 16.4, about 16.5, about 16.6, about 16.7, about 16.8, about 16.9, about 17.0, or any value range of values between any two of these values.

[0104] The method further comprises contacting the Ita cage containing aluminosilicate zeolite composition with a combustion exhaust stream wherein the combustion exhaust stream comprises nitrous oxide. This allows the Ita cage containing aluminosilicate zeolite composition to remove the nitrous oxide from the exhaust stream. The combustion exhaust stream may be from any source. In some embodiments, the combustion exhaust stream is from an internal combustion engine.

[0105] In some embodiments, the combustion exhaust stream has a temperature of about 100 °C, about 110 °C, about 120 °C, about 130 °C, about 140 °C, about 150 °C, about 160 °C, 19ACTIVE\ 1627190097.1about 170 °C, about 180 °C, about 190 °C, about 200 °C, about 210 °C, about 220 °C, about 230 °C, about 240 °C, about 250 °C, about 260 °C, about 270 °C, about 280 °C, about 290 °C, about 300 °C, about 310 °C, about 320 °C, about 330 °C, about 340 °C, about 350 °C, about 360 °C, about 370 °C, about 380 °C, about 390 °C, about 400 °C, about 410 °C, about 420 °C, about 430 °C, about 440 °C, about 450 °C, about 460 °C, about 470 °C, about 480 °C, about 490 °C, about 500 °C, or any value or range of values between any two of these values. In some embodiments, the combustion exhaust stream has a temperature of about 200 °C to about 500 °C, about 250 °C to about 400 °C, or about 300°C to about 350 °C.

[0106] In some embodiments, a method comprises removing CO2 from a gaseous stream. In some embodiments, the gaseous stream comprises one of industrial flue gas, HVAC air streams, or an air stream for the direct air capture of CO2. In some embodiments, the method of removing CO2 from a gaseous stream comprises providing an Ita cage containing aluminosilicate zeolite composition. In some embodiments, the Ita cage containing aluminosilicate zeolite composition has a SAR greater than about 10.5. In some embodiments, the Ita cage containing aluminosilicate zeolite composition has a SAR greater than about 12. In some embodiments, the Ita cage containing aluminosilicate zeolite composition comprises one of a KFI zeolite, a UFI zeolite, an RHO zeolite, or an LTA zeolite. The Ita cage containing aluminosilicate zeolite composition may contain similar properties as the Ita cage containing aluminosilicate zeolite compositions described above.

[0107] The method further comprises contacting the Ita cage containing aluminosilicate zeolite composition with the gaseous stream comprising CO2. This allows the Ita cage containing aluminosilicate zeolite composition to remove the CO2 from the gaseous stream. The gaseous stream comprising CO2 may be from any source. In some embodiments, the gaseous stream comprises one of industrial flue gas, HVAC air streams, or an air stream for the direct air capture of CO2.

[0108] Selective Catalytic Reduction (SCR) Catalysts

[0109] Selective catalytic reduction (SCR) catalysts may be assembled using the abovedescribed Ita-cage containing aluminosilicate zeolite compositions.

[0110] In some embodiments, the SCR catalyst comprises comprising a Ita cage containing aluminosilicate zeolite composition a molar ratio of silica-to-alumina (SAR) of the composition greater than about 12. In some embodiments, the Ita cage containing aluminosilicate zeolite composition is synthesized by providing an alumina source, a silica source, and an organic structure directing agent comprising a heterocyclic aza-crown ether, mixing the alumina source, silica source, and organic structure directing agent to create a 20ACTIVE\ 1627190097.1synthesizing mixture, and subjecting the synthesizing mixture to crystallization conditions to form an aluminosilicate zeolite.[oni] In some embodiments, the Ita cage containing aluminosilicate zeolite composition further comprises a promoter metal. The promoter metal may be present in the Ita cage containing aluminosilicate zeolite composition in any amount effective for the removal of nitrogen oxides from a gaseous stream. In some embodiments, the promoter metal is present in an amount based on the total weight of the SCR catalyst of about 1.0 wt. %, about 2.0 wt. %, about 3.0 wt. %, about 4.0 wt. %, about 5.0 wt. %, about 6.0 wt. %, about 7.0 wt. %, about 8.0 wt. %, about 9.0 wt. %, about 10.0 wt. %, or any value range of values between any two of these values. In some embodiments, the promoter metal is present in an amount based on the total weight of the SCR catalyst of about 1.0 wt. % to about 10 wt. %. In some embodiments, the promoter metal is present in an amount based on the total weight of the SCR catalyst of about 4 wt. % to about 6 wt. %. In some embodiments, the promoter metal weight percent is calculated using the weight of the metal oxide._In some embodiments, the promoter metal is selected from iron, copper, and combinations thereof. In some embodiments, the promoter metal comprises one or more of Fe20s or CuO.

[0112] The present disclosure includes the following embodiments. These embodiments may be combined in any manner to form new embodiments.1. A method comprising: providing an alumina source, a silica source, and an organic structure directing agent comprising a heterocyclic aza-crown ether; mixing the alumina source, silica source, and organic structure directing agent to create a synthesizing mixture; and subjecting the synthesizing mixture to crystallization conditions to form an aluminosilicate zeolite, wherein the Ita cage containing aluminosilicate zeolite composition has a molar ratio of silica-to-alumina (SAR) of the composition greater than about 8.2. The method of embodiment 1, wherein the Ita cage containing aluminosilicate zeolite composition comprises one of an RHO zeolite, KFI zeolite, LTA zeolite, or UFI zeolite.3. The method of either of embodiments 1 or 2, wherein the heterocyclic aza-crown ether is 4,7,13,16,21 ,24-Hexaoxa- 1 , 10-diazabicyclo[8.8.8]hexacosane.4. The method of any of embodiments 1-3, further comprising: providing at least one cation source; and mixing the at least one cation source into the synthesizing mixture, wherein the at least one cation source comprises one or more of tetramethylammonium, sodium, cesium, potassium, and strontium.21ACTIVE\ 1627190097.15. The method of any of embodiments 1-3, wherein the Ita cage containing aluminosilicate zeolite composition comprises an RHO zeolite with a SAR of greater than about 8 and wherein the composition is substantially free of fluoride.6. The method of any of embodiments 1-3, wherein the Ita cage containing aluminosilicate zeolite composition comprises a UFI zeolite with a SAR of greater than about 14 and wherein the composition is substantially free of fluoride.7. The method of any of embodiments 1-3, wherein the Ita cage containing aluminosilicate zeolite composition comprises a KFI zeolite with a SAR of greater than about 10.5.8. The method of any of embodiments 1-3, wherein the Ita cage containing aluminosilicate zeolite composition comprises an LTA zeolite with a SAR of greater than about 14 and wherein the composition is substantially free of fluoride.9. The method of any of embodiments 1-3, wherein the Ita cage containing aluminosilicate zeolite composition comprises a KFI zeolite and wherein the KFI zeolite has a unit cell volume less than about 6500 A3.10. The method of any of embodiments 1-3, wherein the Ita cage containing aluminosilicate zeolite composition comprises a KFI zeolite and wherein the KFI zeolite has a unit cell volume less than about 6480 A3.11. The method of any of embodiments 1-3, wherein the Ita cage containing aluminosilicate zeolite composition comprises an RHO zeolite and wherein the RHO zeolite has a unit cell volume of less than about 3325 A3.12. The method of any of embodiments 1-3, wherein the Ita cage containing aluminosilicate zeolite composition comprises an RHO zeolite and wherein the RHO zeolite has a unit cell volume of less than about 3320 A3.13. The method of any of embodiments 1-3, wherein the Ita cage containing aluminosilicate zeolite composition comprises a UFI zeolite and wherein the UFI zeolite has a unit cell volume less than about 4200 A3.14. The method of any of embodiments 1-3, wherein the Ita cage containing aluminosilicate zeolite composition comprises a UFI zeolite and wherein the UFI zeolite has a unit cell volume less than about 4190 A3.22ACTIVE\ 1627190097.115. An Ita cage containing aluminosilicate zeolite composition comprising: a molar ratio of silica-to-alumina (SAR) of the composition greater than about 8; wherein the Ita cage containing aluminosilicate zeolite composition is synthesized by; providing an alumina source, a silica source, and an organic structure directing agent comprising a heterocyclic aza-crown ether; mixing the alumina source, silica source, and organic structure directing agent to create a synthesizing mixture; and subjecting the synthesizing mixture to crystallization conditions to form an aluminosilicate zeolite.16. The Ita cage containing aluminosilicate zeolite composition of embodiment 15, wherein the organic structure directing agent comprises 4,7,13,16,21,24-Hexaoxa-l,10- diazabicyclo[8.8.8]hexacosane.17. The Ita cage containing aluminosilicate zeolite composition of either of embodiments 15 or 16, wherein the Ita cagecontaining aluminosilicate zeolite composition comprises one of an RHO zeolite, KFI zeolite, LTA zeolite, or UFI zeolite.18. The Ita cage containing aluminosilicate zeolite composition of any of embodiments 15-17, wherein the Ita cage containing aluminosilicate zeolite composition comprises an RHO zeolite with a SAR of greater than about 8 and wherein the composition is substantially free of fluoride.19. The Ita cage containing aluminosilicate zeolite composition of any of embodiments 15-17, wherein the Ita cage containing aluminosilicate zeolite composition comprises a UFI zeolite with a SAR of greater than about 14 and wherein the composition is substantially free of fluoride.20. The Ita cage containing aluminosilicate zeolite composition of any of embodiments 15-17, wherein the Ita cage containing aluminosilicate zeolite composition comprises an LTA zeolite with a SAR of greater than about 14 and wherein the composition is substantially free of fluoride.21. The Ita cage containing aluminosilicate zeolite composition of any of embodiments 15-17, wherein the Ita cage containing aluminosilicate zeolite composition comprises an KFI zeolite with a SAR of greater than about 10.5.22. The Ita cage containing aluminosilicate zeolite composition of any of embodiments 15-17 comprising a KFI zeolite with a unit cell volume less than about 6500 A3.23ACTIVE\ 1627190097.123. The Ita cage containing aluminosilicate zeolite composition of any of embodiments 15-17 comprising an RHO zeolite with a unit cell volume of less than about 3325 A3.24. The Ita cage containing aluminosilicate zeolite composition of any of embodiments 15-17 comprising a UFI zeolite with a unit cell volume less than about 4200 A3.25. An Ita cage containing aluminosilicate zeolite precursor composite comprising: a molar ratio of silica-to-alumina (SAR) of the composition greater than about 8; and a plurality of unit cells, wherein each of the plurality of unit cells comprises: an Ita cage; and an amount of an organic structure directing agent positioned within the Ita cage.26. The Ita cage containing aluminosilicate zeolite precursor composite of embodiment 25, wherein the organic structure directing agent comprises a heterocyclic aza-crown ether.27. The Ita cage containing aluminosilicate zeolite precursor composite of either of embodiments 25 or 26, wherein the organic structure directing agent comprises 4,7,13,16,21 ,24-Hexaoxa- 1 , 10-diazabicyclo[8.8.8]hexacosane.28. The Ita cage containing aluminosilicate zeolite precursor composite of any of embodiments 25-27, wherein the containing aluminosilicate zeolite composition comprises one of an RHO zeolite, KFI zeolite, LTA zeolite, or UFI zeolite.29. The Ita cage containing aluminosilicate zeolite precursor composite of any of embodiments 25-27, wherein the Ita cage containing aluminosilicate zeolite composition is substantially free of fluoride.30. The Ita cage containing aluminosilicate zeolite precursor composite of any of embodiments 25-27, wherein the Ita cage containing aluminosilicate zeolite composition comprises an RHO zeolite with a SAR of greater than about 8 and wherein the composition is substantially free of fluoride.31. The Ita cage containing aluminosilicate zeolite precursor composite of any of embodiments 25-27, wherein the Ita cage containing aluminosilicate zeolite composition comprises a UFI zeolite with a SAR of greater than about 14 and wherein the composition is substantially free of fluoride.32. The Ita cage containing aluminosilicate zeolite precursor composite of any of embodiments 25-27, wherein the Ita cage containing aluminosilicate zeolite composition comprises an24ACTIVE\ 1627190097.1LTA zeolite with a SAR of greater than about 14 and wherein the composition is substantially free of fluoride.33. The Ita cage containing aluminosilicate zeolite precursor composite of any of embodiments 25-27, wherein the Ita cage containing aluminosilicate zeolite composition comprises an KFI zeolite with a SAR of greater than about 10.5.34. An adsorbent material effective for the removal of CO2 from a gaseous stream, the adsorbent material comprising the Ita cage containing aluminosilicate zeolite composition of any one of embodiments 15 to 24.35. A method of removing CO2 from a gaseous stream, the method comprising: providing the Ita cage containing aluminosilicate zeolite composition of any one of claims 15 to 24; and contacting the Ita cage containing aluminosilicate zeolite composition with the gaseous stream comprising CO2.36. The method of embodiment 35, wherein the gaseous stream comprises one of industrial flue gas, HVAC air streams, or an air stream for the direct air capture of CO2.37. A selective catalytic reduction (SCR) catalyst effective for the abatement of nitrogen oxides (NOx) in an exhaust gas stream, the SCR catalyst comprising the Ita cage containing aluminosilicate zeolite composition of any one of embodiments 15 to 24, wherein the Ita cage containing aluminosilicate zeolite composition comprises a promoter material.38. The SCR catalyst of embodiment 37, wherein the promoter metal is present in an amount of about 1.0 wt. % to about 10 wt. %, based on the total weight of the SCR catalyst, and calculated as the metal oxide.39. The SCR catalyst of embodiment 37, wherein the promoter metal is present in an amount of about 3 wt. % to about 6 wt. %.40. The SCR catalyst of any of embodiments 37-39, wherein the promoter metal is selected from iron, copper, and combinations thereof.41. A method of removing nitrogen oxides (NOX) from a combustion engine exhaust, the method comprising: providing the SCR catalyst of any one of embodiments 37 to 40; and contacting the SCR catalyst with a combustion engine exhaust stream wherein the combustion engine exhaust stream comprises NOX25ACTIVE\ 1627190097.1EXAMPLES

[0113] Example 1 : KFI Zeolite Synthesis

[0114] Zeolite syntheses using 4,7,13,16,21,24-Hexaoxa-l,10-diazabicyclo[8.8.8]hexacosane (Kryptofix 222, 98%, TCI) were performed using synthesis mixture combining colloidal silica (Ludox HS-40, 40%, Aldrich), Al powder (97.5%, 3-4.5 pm, TCI), KOH (45% aqueous solution, Aldrich), Sr(NOs)2 (98%, Thermo Fisher Scientific), and deionized water. The composition of the final synthesis mixture of samples (1), (3), (4), (6), and (7) was 1.0R-xK20-0.1Sr(N03)2-yA1203-10.0Si02’230H20, where R is the Kryptofix 222, and where x and y are varied between 2.0 < x < 2.5 and 1.0 < y < 0.5, respectively. Samples (2) and (3) had a final composition mixture of 1.0R-xK20-yA1203-10.0Si02’230H20, where R is the Kryptofix 222, and where x and y are varied between 2.0 < x < 2.5 and 1.0 < y < 0.5, respectively. In sample (7), a small amount (4 wt % with respect of the silica in the gel) of KFI seed crystals (ZK-5 crystals) in the proton form was added as seeds to the synthesis mixture. In a typical synthesis of KFI-type zeolite with Si / Al = 4.8, 0.11 g of Al powder was first mixed with 1.00 g of KOH solutions in 5.95 g of distilled water. To the resulting clear solution, 3.00 g of Ludox HS-40 and 0.77 g of Kryptofix 222 were added. Then, 0.04 g of Sr(NOs)2 was added to the synthesis mixture. The composition of the resulting gel was 1.0R-2.0K20-0.1Sr(N03)2’1.0A1203-10.0Si02’230H20. The final synthesis mixture was stirred at room temperature for 1 day, charged into Teflon-lined 23 -ml autoclaves and, heated at 150 °C under static conditions for 7 days. Similarly, the synthesis of KFI-type zeolite with Si / Al = 7.4 was as follows: 0.05 g of Al powder was first mixed with 1.00 g of KOH solutions in 5.89 g of distilled water. To the resulting clear solution, 3.00 g of Ludox HS-40 and 0.77 g of Kryptofix 222 were added. Then, 0.04 g of Sr(NOs)2 was added to the synthesis mixture. Then, 0.12 g of the previously prepared proton forms of ZK-5 (Si / Al=4.8) seed crystals were added to the gel. The resulting gel composition was 1.0R-2.0K20-0.1Sr(N03)2’0.5A1203-10.0Si02’230H20. The final synthesis mixture was stirred at room temperature for 1 day, charged into Teflon-lined 23-ml autoclaves and heated at 150 °C under static for 5 days.

[0115] The solid product was recovered by filtration or centrifugation (11000 rpm, 5 min), repeatedly washed with deionized water, and dried overnight at room temperature. The samples were calcined at 550 °C in air for 8 h to remove the occluded organic SDAs. The calcined KFI- type zeolites were refluxed twice in 1.0 M NH4NO3 solutions at 80 °C for 6 h (1.0 g solid per 100 ml solution). The proton form of KFI-type zeolites was prepared by calcination of the NH4+-exchanged KFI-type zeolite in air at 500 °C for 4 h.26ACTIVE\ 1627190097.1

[0116] Aluminum and silicon contents were determined using inductively coupled plasma atomic emission spectroscopy (ICP-AES, Agilent 5100). 10 mg of zeolite were placed in a polyethylene microfuge tube (1.5 mL) and digested in 10 pL hydrofluoric acid (48 wt %, trace metals basis, Sigma-Aldrich) for 1 day. The hydrofluoric acid solution was diluted to a total mass of 10.0 g using 2 wt % aqueous nitric acid (HNO3) (veritas purity, GFS Chemicals). A six-point calibration curve was built using ICP standard solutions of 1,000 ppm Al in 2 wt% HNO3 and 1,000 ppm Si in 2 wt% HNO3. All standard solutions were purchased from Sigma- Aldrich (TraceCERT). The crystal structures of zeolite catalysts were determined from powder x-ray diffraction (PXRD) patterns collected using a Bruker D8 diffractometer using Cu-Ka radiation (1 = 1.5418 A, 40 kV, 40 mA). Data were recorded in the range of 5-25 26 with an angular step size of 0.02° and a rate of 5° min'1.

[0117] Information regarding the testing samples, the elemental analysis, and the powder- x- ray diffraction data is presented below in TABLE 1.TABLE 1

[0118] The elemental analysis data showed that increasing Si / Al ratio in the synthesis gel, while keeping the BGO / SiCL ratio (2.0) constant directed no crystallization of zeolite. However, when adding a small amount (4 wt. % of the silica in the gel) of previously prepared proton forms of KFI-type crystals as seeds to the above synthetic mixture, a pure KFI zeolite structure was obtained with an increased Si / Al of 7.4. FIG. 7 depicts the PXRD data of samples (1), (4), and (7) as compared to a simulated KFI zeolite 701. The PXRD patterns in reveal that the KFI zeolites are highly crystalline and phase-pure, and no reflections other than those from the corresponding zeolite are observed.

[0119] Nuclear magnetic resonance (NMR) testing was performed on KFI zeolite samples with an Si / Al ratio of 5.5 and 3.5. Experiments for both 29Si and 27A1 magic angle spinning (MAS)27ACTIVE\ 1627190097.1NMR were run on samples pretreated at 80+% humidity at room temperature for at least 48 hours in a hydrating chamber. 29Si tests were run on a 400MHz Varian spectrometer running with a sample spin rate of 3500Hz, with frequency referenced to TMS utilizing a secondary solid reference of Kaolin, with a 90° excitation pulse to obtain 64 transients. 27A1 spectra were obtained on a 600MHz Agilent DD2 spectrometer with a sample spin rate of 18kHz with frequency referenced to Al(H2O)e3+using a 15° excitation pulse to obtain 4000 transients. The results of the 29Si and 27A1 MAS NMR testing for the KFI zeolite sample with an Si / Al ratio of 5.5 are provided in FIGS. 8A and 8B, respectively, while the results of the 29Si and 27A1 MAS NMR testing for the KFI zeolite sample with an Si / Al ratio of 5.5 are provided in FIGS. 8C and 8D, respectively.

[0120] Example 2: RHO, LTA, and UFI Zeolite Synthesis

[0121] Zeolite syntheses using 4,7,13,16,21,24-Hexaoxa-l,10-diazabicyclo[8.8.8]hexacosane (Kryptofix 222, 98%, TCI) and tetramethylammonium hydroxide pentahydrate (TMAOH 5H2O, 97%, Aldrich) were performed using synthesis mixture combining colloidal silica (Ludox AS-40, 40 wt%, Aldrich), Aluminum hydroxide (Al(OH)s, 100%, SPI Pharmacy 0250-110), Sodium hydroxide (50 wt% aqueous solution, Aldrich), Cesium hydroxide (50 wt% aqueous solution, Aldrich), and deionized water. For LTA syntheses, the composition of the final synthesis mixture was in the form of xR: yNa2O: O.O25TMA2O: ZAI2O3: LOSiCL: I5H2O, where R is the Kryptofix 222, and where x, y, and z are varied between 0.1 < x < 0.35, 0.025 < y < 0.1, and 0.02 < z < 0.05 respectively. For UFI syntheses, the composition of the final synthesis mixture was in the form of xR: yNa2O: O.O25TMA2O: ZAI2O3: l.OSiCL: I5H2O, where x, y, and z are varied between 0.15 < x < 0.35, 0.1 < y < 0.15, and 0.03 < z < 0.05 respectively. For RHO syntheses, the composition of the final synthesis mixture was in the form of 0.05R: yNa2O: O.O3CS2O: ZAI2O3: 1.0SiO2: I5H2O, where x, y, and z are varied between 0.18 < y < 0.25, and 0.01 < z < 0.1 respectively. To accelerate the crystallization kinetics, a small amount (4 wt % with respect to the silica in the gel) of the target material crystals in the proton form were added as seeds to the synthesis mixture.

[0122] In a typical synthesis of LTA-type zeolite with Si / Al = 12.8, 0.04 g of Al(0H)3 powder was first mixed with 0.08g of NaOH solutions and 0.05 g of TMAOH solution in 0.86g of distilled water. To the resulting clear solution, 0.75g of Ludox AS-40 and 0.67g of K222 were added. 4 wt% of proton-exchanged LTA zeolite (Si / Al = 23) were added as seed material. The composition of the resulting gel was 0.35R: 0.1Na2O: O.O25TMA2O: O.O5AI2O3: LOSiCL: I5H2O. The final synthesis mixture was stirred at room temperature for 1 day, transferred to Teflon-lined 23 -ml autoclaves and, heated at 175 °C under either static or dynamic condition 28ACTIVE\ 1627190097.1for 14 days. Similarly, the synthesis of UFI-type zeolite with Si / Al = 14.0 was as follows: 0.04g of Al(0H)3 powder was first mixed with 0.08g of NaOH solutions and 0.05g of TMAOH solution in 0.86g of distilled water. To the resulting clear solution, 0.75g of Ludox AS-40 and 0.29g of K222 were added. Then, 0.03g of the previously prepared proton forms of UFI (Si / Al=14.0) seed crystals were added to the gel. The resulting gel composition was 0.15R: 0.05Na20: 0.025TMA20: O.O5AI2O3: LOSiCL: I5H2O. The final synthesis mixture was stirred at room temperature for 1 day, transferred to Teflon-lined 23 -ml autoclaves and heated at 175 °C under either static or dynamic for 7 days. Finally, the synthesis of RHO-type zeolite with Si / Al = 10.9 was as follows: 0.05g of Al metal powder was first mixed with 1.16g of NaOH solution and 0.65g of CsOH solution in 5.44g of distilled water. After all the hydrogen gas is emitted and the solution becomes clear, 0.70g of K222 were added. Then, 5.46g of Ludox HS-40 were slowly added to the solution. 4 wt% of proton-exchanged RHO seed (Si / Al = 10) were added to the solution. The composition of the resulting gel was 0.05R: 0.2Na2O: O.O3CS2O: O.O25AI2O3: ISiCL: I5H2O. The final synthesis mixture was stirred at room temperature for 1 day, transferred to Teflon-lined 23-ml autoclaves and, heated at 110 °C for 14 days.

[0123] The solid product was recovered by filtration or centrifugation (11000 rpm, 5 min), repeatedly washed with deionized water, and dried overnight at room temperature. The samples were ramped with 1 °C / min and calcined at 580 °C in air for 6 h to remove the occluded organic SDAs. The calcined zeolites were refluxed twice in 1.0 M NH4NO3 solutions at 80 °C for 6 h (1.0 g solid per 100 ml solution). The proton form of zeolites was prepared by calcination of the NH4+-exchanged zeolite in air at 500 °C for 4 h.

[0124] Aluminum and silicon contents were determined using inductively coupled plasma atomic emission spectroscopy (ICP-AES, Agilent 5100). 10 mg of zeolite were placed in a polyethylene microfuge tube (15 mL) and digested in 10 pL hydrofluoric acid (48 wt %, trace metals basis, Sigma-Aldrich) for 1 day. The hydrofluoric acid solution was diluted to a total mass of 10.0 g using 2 wt % aqueous nitric acid (HNO3) (veritas purity, GFS Chemicals). A six-point calibration curve was built using ICP standard solutions of 1,000 ppm Al, 1,000 ppm Si, 1,000 ppm Na, and 1,000 ppm K in 2 wt% HNO3. All standard solutions were purchased from Sigma-Aldrich (TraceCERT).

[0125] The crystal structures of zeolite catalysts were determined from powder x-ray diffraction patterns collected using a Bruker D8 diffractometer using Cu-Ka radiation (1 = 1.5418 A, 40 kV, 40 mA). Data were recorded in the range of 5 - 45° 26 with an angular step size of 0.02° and a rate of 5° min'1.29ACTIVE\ 1627190097.1

[0126] Nuclear magnetic resonance (NMR) testing was performed on RHO zeolite samples and a Kryptofix 222 control sample. Experiments for 1H-13C spectra were run on a sample pretreated at 80+% humidity at room temperature for at least 48 hours in a hydrating chamber and a sample that did not undergo pretreating. Experiments for 1H-13C spectra utilized a CPMAS pulse sequence with 3ms contact time and high power 1H decoupling, spun at 5kHz on a 600MHz Agilent DD2 spectrometer. Frequency of the obtained is referenced to TMS with 8000 transients. The results of the 1H-13C spectra testing for the pretreated RHO zeolite sample are provided in FIG. 9 A, while the results of the 1H-13C spectra testing for the RHO zeolite sample that was not pretreated are provided in FIG. 9B and the results of the 1H-13C spectra testing for the Kryptofix 222 control sample are provided in FIG. 9C.

[0127] FIG. 8 depicts the PXRD data from the synthesized LTA zeolite and FIG. 11 depicts a scanning electron microscope (SEM) image of the synthesized LTA zeolite. The PXRD data shows a clear LTA framework as compared to a reference LTA sample. Additionally, the SEM image shows a cube-like morphology of the LTA zeolite. The elemental analysis of the LTA zeolite provided a SAR of 12.8. FIG. 12 provides a graphical representation of the SAR of the synthesized LTA zeolite as compared to previous LTA zeolite compositions.

[0128] FIG. 13 depicts the PXRD data from the synthesized RHO zeolite and FIG. 14 depicts a SEM image of the synthesized RHO zeolite. The PXRD data shows a clear RHO framework as compared to a reference RHO sample. Additionally, the SEM image shows a rhombic dodecahedron morphology of the RHO zeolite. The elemental analysis of the RHO zeolite provided a SAR of 10.9. FIG. 15 provides a graphical representation of the SAR of the synthesized RHO zeolite as compared to previous RHO zeolite compositions.

[0129] FIG. 16 depicts the PXRD data from the synthesized UFI zeolite and FIG. 17 depicts a SEM image of the synthesized UFI zeolite. The PXRD data shows a clear UFI framework as compared to a reference UFI sample. Additionally, the SEM image shows a plate-like morphology of the UFI zeolite. The elemental analysis of the UFI zeolite provided a SAR of 14.0. FIG. 18 provides a graphical representation of the SAR of the synthesized UFI zeolite as compared to previous UFI zeolite compositions.

[0130] Various of the above-disclosed and other features and functions, or alternatives thereof, may be combined into many other different systems or applications. Various presently unforeseen or unanticipated alternatives, modifications, variations or improvements therein may be subsequently made by those skilled in the art, each of which is also intended to be encompassed by the disclosed embodiments.30ACTIVE\ 1627190097.1

Claims

CLAIMS1. A method of synthesizing an Ita cage containing aluminosilicate zeolite composition, the method comprising: providing an alumina source, a silica source, and an organic structure directing agent comprising a heterocyclic aza-crown ether; mixing the alumina source, silica source, and organic structure directing agent to create a synthesizing mixture; and subjecting the synthesizing mixture to crystallization conditions to form an aluminosilicate zeolite, wherein the Ita cage containing aluminosilicate zeolite composition has a molar ratio of silica-to-alumina (SAR) of the composition greater than about 8.

2. The method of claim 1, wherein the Ita cage containing aluminosilicate zeolite composition comprises one of an RHO zeolite, KFI zeolite, LTA zeolite, or UFI zeolite.

3. The method of claim 1, wherein the heterocyclic aza-crown ether is 4,7,13,16,21,24- Hexaoxa-l,10-diazabicyclo[8.8.8]hexacosane.

4. The method of claim 1, further comprising: providing at least one cation source; and mixing the at least one cation source into the synthesizing mixture, wherein the at least one cation source comprises one or more of tetramethylammonium, sodium, cesium, potassium, and strontium.

5. The method of claim 1, wherein the Ita cage containing aluminosilicate zeolite composition comprises an RHO zeolite with a SAR of greater than about 8 and wherein the composition is substantially free of fluoride.

6. The method of claim 1, wherein the Ita cage containing aluminosilicate zeolite composition comprises a UFI zeolite with a SAR of greater than about 14 and wherein the composition is substantially free of fluoride.

7. The method of claim 1, wherein the Ita cage containing aluminosilicate zeolite composition comprises a KFI zeolite with a SAR of greater than about 10.5.

8. The method of claim 1, wherein the Ita cage containing aluminosilicate zeolite composition comprises an LTA zeolite with a SAR of greater than about 14 and wherein the composition is substantially free of fluoride.31ACTIVE\ 1627190097.

19. The method of claim 1, wherein the Ita cage containing aluminosilicate zeolite composition comprises a KFI zeolite and wherein the KFI zeolite has a unit cell volume less than about 6500 A3.

10. The method of claim 1, wherein the Ita cage containing aluminosilicate zeolite composition comprises a KFI zeolite and wherein the KFI zeolite has a unit cell volume less than about 6480 A3.

11. The method of claim 1, wherein the Ita cage containing aluminosilicate zeolite composition comprises an RHO zeolite and wherein the RHO zeolite has a unit cell volume of less than about 3325 A3.

12. The method of claim 1, wherein the Ita cage containing aluminosilicate zeolite composition comprises an RHO zeolite and wherein the RHO zeolite has a unit cell volume of less than about 3320 A3.

13. The method of claim 1, wherein the Ita cage containing aluminosilicate zeolite composition comprises a UFI zeolite and wherein the UFI zeolite has a unit cell volume less than about 4200 A3.

14. The method of claim 1, wherein the Ita cage containing aluminosilicate zeolite composition comprises a UFI zeolite and wherein the UFI zeolite has a unit cell volume less than about 4190 A3.

15. An Ita cage containing aluminosilicate zeolite composition comprising: a molar ratio of silica-to-alumina (SAR) of the composition greater than about 8; wherein the Ita cage containing aluminosilicate zeolite composition is synthesized by; providing an alumina source, a silica source, and an organic structure directing agent comprising a heterocyclic aza-crown ether; mixing the alumina source, silica source, and organic structure directing agent to create a synthesizing mixture; and subjecting the synthesizing mixture to crystallization conditions to form an aluminosilicate zeolite.32ACTIVE\ 1627190097.

116. The Ita cage containing aluminosilicate zeolite composition of claim 15, wherein the organic structure directing agent comprises 4,7,13,16,21,24-Hexaoxa-l,10- diazabicyclo[8.8.8]hexacosane.

17. The Ita cage containing aluminosilicate zeolite composition of claim 15, wherein the Ita cagecontaining aluminosilicate zeolite composition comprises one of an RHO zeolite, KFI zeolite, LTA zeolite, or UFI zeolite.

18. The Ita cage containing aluminosilicate zeolite composition of claim 15, wherein the Ita cage containing aluminosilicate zeolite composition comprises an RHO zeolite with a SAR of greater than about 8 and wherein the composition is substantially free of fluoride.

19. The Ita cage containing aluminosilicate zeolite composition of claim 15, wherein the Ita cage containing aluminosilicate zeolite composition comprises a UFI zeolite with a SAR of greater than about 14 and wherein the composition is substantially free of fluoride.

20. The Ita cage containing aluminosilicate zeolite composition of claim 15, wherein the Ita cage containing aluminosilicate zeolite composition comprises an LTA zeolite with a SAR of greater than about 14 and wherein the composition is substantially free of fluoride.

21. The Ita cage containing aluminosilicate zeolite composition of claim 15, wherein the Ita cage containing aluminosilicate zeolite composition comprises an KFI zeolite with a SAR of greater than about 10.5.

22. The Ita cage containing aluminosilicate zeolite composition of claim 15 comprising a KFI zeolite with a unit cell volume less than about 6500 A3.

23. The Ita cage containing aluminosilicate zeolite composition of claim 15 comprising an RHO zeolite with a unit cell volume of less than about 3325 A3.

24. The Ita cage containing aluminosilicate zeolite composition of claim 15 comprising a UFI zeolite with a unit cell volume less than about 4200 A3.

25. An Ita cage containing aluminosilicate zeolite precursor composite comprising: a molar ratio of silica-to-alumina (SAR) of the composition greater than about 8; and a plurality of unit cells, wherein each of the plurality of unit cells comprises: an Ita cage; and33ACTIVE\ 1627190097.1an amount of an organic structure directing agent positioned within the Ita cage.

26. The Ita cage containing aluminosilicate zeolite precursor composite of claim 25, wherein the organic structure directing agent comprises a heterocyclic aza-crown ether.

27. The Ita cage containing aluminosilicate zeolite precursor composite of claim 25, wherein the organic structure directing agent comprises 4,7,13,16,21,24-Hexaoxa-l,10- diazabicyclo[8.8.8]hexacosane.

28. The Ita cage containing aluminosilicate zeolite precursor composite of claim 25, wherein the containing aluminosilicate zeolite composition comprises one of an RHO zeolite, KFI zeolite, LTA zeolite, or UFI zeolite.

29. The Ita cage containing aluminosilicate zeolite precursor composite of claim 26, wherein the Ita cage containing aluminosilicate zeolite composition is substantially free of fluoride.

30. The Ita cage containing aluminosilicate zeolite precursor composite of claim 25, wherein the Ita cage containing aluminosilicate zeolite composition comprises an RHO zeolite with a SAR of greater than about 8 and wherein the composition is substantially free of fluoride.

31. The Ita cage containing aluminosilicate zeolite precursor composite of claim 25, wherein the Ita cage containing aluminosilicate zeolite composition comprises a UFI zeolite with a SAR of greater than about 14 and wherein the composition is substantially free of fluoride.

32. The Ita cage containing aluminosilicate zeolite precursor composite of claim 25, wherein the Ita cage containing aluminosilicate zeolite composition comprises an LTA zeolite with a SAR of greater than about 14 and wherein the composition is substantially free of fluoride.

33. The Ita cage containing aluminosilicate zeolite precursor composite of claim 25, wherein the Ita cage containing aluminosilicate zeolite composition comprises an KFI zeolite with a SAR of greater than about 10.5.

34. An adsorbent material effective for the removal of CO2 from a gaseous stream, the adsorbent material comprising the Ita cage containing aluminosilicate zeolite composition of any one of claims 15 to 24.34ACTIVE\ 1627190097.

135. A method of removing CO2 from a gaseous stream, the method comprising: providing the Ita cage containing aluminosilicate zeolite composition of any one of claims 15 to 24; and contacting the Ita cage containing aluminosilicate zeolite composition with the gaseous stream comprising CO2.

36. The method of claim 35, wherein the gaseous stream comprises one of industrial flue gas, HVAC air streams, or an air stream for the direct air capture of CO2.

37. A selective catalytic reduction (SCR) catalyst effective for the abatement of nitrogen oxides (NOx) in an exhaust gas stream, the SCR catalyst comprising the Ita cage containing aluminosilicate zeolite composition of any one of claims 15 to 24, wherein the Ita cage containing aluminosilicate zeolite composition comprises a promoter material.

38. The SCR catalyst of claim 37, wherein the promoter metal is present in an amount of about 1.0 wt. % to about 10 wt. %, based on the total weight of the SCR catalyst, and calculated as the metal oxide.

39. The SCR catalyst of claim 37, wherein the promoter metal is present in an amount of about 3 wt. % to about 6 wt. %.

40. The SCR catalyst of any of claims 37 to 39, wherein the promoter metal is selected from iron, copper, and combinations thereof.

41. A method of removing nitrogen oxides (NOX) from a combustion engine exhaust, the method comprising: providing the SCR catalyst of any one of claims 37 to 40; and contacting the SCR catalyst with a combustion engine exhaust stream wherein the combustion engine exhaust stream comprises NOX.35ACTIVE\ 1627190097.1

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