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      Two-Dimensional Zeolite Materials: Structural and Acidity Properties

      review-article
      , , *
      Materials
      MDPI
      2D zeolite, layered zeolite, zeolite structure, Brønsted acidity, Lewis acidity

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          Abstract

          Zeolites are generally defined as three-dimensional (3D) crystalline microporous aluminosilicates in which silicon (Si 4+) and aluminum (Al 3+) are coordinated tetrahedrally with oxygen to form large negative lattices and consequent Brønsted acidity. Two-dimensional (2D) zeolite nanosheets with single-unit-cell or near single-unit-cell thickness (~2–3 nm) represent an emerging type of zeolite material. The extremely thin slices of crystals in 2D zeolites produce high external surface areas (up to 50% of total surface area compared to ~2% in micron-sized 3D zeolite) and expose most of their active sites on external surfaces, enabling beneficial effects for the adsorption and reaction performance for processing bulky molecules. This review summarizes the structural properties of 2D layered precursors and 2D zeolite derivatives, as well as the acidity properties of 2D zeolite derivative structures, especially in connection to their 3D conventional zeolite analogues’ structural and compositional properties. The timeline of the synthesis and recognition of 2D zeolites, as well as the structure and composition properties of each 2D zeolite, are discussed initially. The qualitative and quantitative measurements on the acid site type, strength, and accessibility of 2D zeolites are then presented. Future research and development directions to advance understanding of 2D zeolite materials are also discussed.

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          Stable single-unit-cell nanosheets of zeolite MFI as active and long-lived catalysts.

          Zeolites-microporous crystalline aluminosilicates-are widely used in petrochemistry and fine-chemical synthesis because strong acid sites within their uniform micropores enable size- and shape-selective catalysis. But the very presence of the micropores, with aperture diameters below 1 nm, often goes hand-in-hand with diffusion limitations that adversely affect catalytic activity. The problem can be overcome by reducing the thickness of the zeolite crystals, which reduces diffusion path lengths and thus improves molecular diffusion. This has been realized by synthesizing zeolite nanocrystals, by exfoliating layered zeolites, and by introducing mesopores in the microporous material through templating strategies or demetallation processes. But except for the exfoliation, none of these strategies has produced 'ultrathin' zeolites with thicknesses below 5 nm. Here we show that appropriately designed bifunctional surfactants can direct the formation of zeolite structures on the mesoporous and microporous length scales simultaneously and thus yield MFI (ZSM-5, one of the most important catalysts in the petrochemical industry) zeolite nanosheets that are only 2 nm thick, which corresponds to the b-axis dimension of a single MFI unit cell. The large number of acid sites on the external surface of these zeolites renders them highly active for the catalytic conversion of large organic molecules, and the reduced crystal thickness facilitates diffusion and thereby dramatically suppresses catalyst deactivation through coke deposition during methanol-to-gasoline conversion. We expect that our synthesis approach could be applied to other zeolites to improve their performance in a range of important catalytic applications.
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            Dispersible exfoliated zeolite nanosheets and their application as a selective membrane.

            Thin zeolite films are attractive for a wide range of applications, including molecular sieve membranes, catalytic membrane reactors, permeation barriers, and low-dielectric-constant materials. Synthesis of thin zeolite films using high-aspect-ratio zeolite nanosheets is desirable because of the packing and processing advantages of the nanosheets over isotropic zeolite nanoparticles. Attempts to obtain a dispersed suspension of zeolite nanosheets via exfoliation of their lamellar precursors have been hampered because of their structure deterioration and morphological damage (fragmentation, curling, and aggregation). We demonstrated the synthesis and structure determination of highly crystalline nanosheets of zeolite frameworks MWW and MFI. The purity and morphological integrity of these nanosheets allow them to pack well on porous supports, facilitating the fabrication of molecular sieve membranes.
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              Synthesis of self-pillared zeolite nanosheets by repetitive branching.

              Hierarchical zeolites are a class of microporous catalysts and adsorbents that also contain mesopores, which allow for fast transport of bulky molecules and thereby enable improved performance in petrochemical and biomass processing. We used repetitive branching during one-step hydrothermal crystal growth to synthesize a new hierarchical zeolite made of orthogonally connected microporous nanosheets. The nanosheets are 2 nanometers thick and contain a network of 0.5-nanometer micropores. The house-of-cards arrangement of the nanosheets creates a permanent network of 2- to 7-nanometer mesopores, which, along with the high external surface area and reduced micropore diffusion length, account for higher reaction rates for bulky molecules relative to those of other mesoporous and conventional MFI zeolites.
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                Author and article information

                Journal
                Materials (Basel)
                Materials (Basel)
                materials
                Materials
                MDPI
                1996-1944
                12 April 2020
                April 2020
                : 13
                : 8
                : 1822
                Affiliations
                Department of Chemical and Biomolecular Engineering, University of Maryland, College Park, MD 20742, USA; ebschul@ 123456umd.edu (E.S.); weiwuwuhan@ 123456gmail.com (W.W.)
                Author notes
                [* ]Correspondence: liud@ 123456umd.edu ; Tel.: +1-301-405-3522; Fax: +1-301-405-0523
                [†]

                The two authors contributed equally to this work.

                Author information
                https://orcid.org/0000-0002-9246-5926
                https://orcid.org/0000-0003-2392-6546
                Article
                materials-13-01822
                10.3390/ma13081822
                7215918
                32290625
                6266bfcc-79f9-4c70-8df5-387d51797bdf
                © 2020 by the authors.

                Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license ( http://creativecommons.org/licenses/by/4.0/).

                History
                : 18 March 2020
                : 08 April 2020
                Categories
                Review

                2d zeolite,layered zeolite,zeolite structure,brønsted acidity,lewis acidity

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