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      Kinetics and Mechanism of the Hydrolysis and Rearrangement Processes within the Assembly–Disassembly–Organization–Reassembly Synthesis of Zeolites

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          Abstract

          The hydrolysis (disassembly, D) and rearrangement (organization, O) steps of the assembly–disassembly–organization–reassembly (ADOR) process for the synthesis of zeolites have been studied. Germanium-rich UTL was subjected to hydrolysis conditions in water to understand the effects of temperature (100, 92, 85, 81, 77, and 70 °C). Samples were taken periodically over an 8–37 h period, and each sample was analyzed by powder X-ray diffraction. The results show that the hydrolysis step is solely dependent on the presence of liquid water, whereas the rearrangement is dependent on the temperature of the system. The kinetics have been investigated using the Avrami–Erofeev model. With increasing temperature, an increase in the rate of reaction for the rearrangement step was observed, and the Arrhenius equation was used to ascertain an apparent activation energy for the rearrangement from the kinetic product of the disassembly (IPC-1P) to the thermodynamic product of the rearrangement (IPC-2P). From this information, a mechanism for this transformation can be postulated.

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          The ADOR mechanism for the synthesis of new zeolites.

          A novel methodology, called ADOR (assembly-disassembly-organisation-reassembly), for the synthesis of zeolites is reviewed here in detail. The ADOR mechanism stems from the fact that certain chemical weakness against a stimulus may be present in a zeolite framework, which can then be utilized for the preparation of new solids through successive manipulation of the material. In this review, we discuss the critical factors of germanosilicate zeolites required for application of the ADOR protocol and describe the mechanism of hydrolysis, organisation and condensation to form new zeolites starting from zeolite UTL. Last but not least, we discuss the potential of this methodology to form other zeolites and the prospects for future investigations.
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            Synthesis of 'unfeasible' zeolites.

            Zeolites are porous aluminosilicate materials that have found applications in many different technologies. However, although simulations suggest that there are millions of possible zeolite topologies, only a little over 200 zeolite frameworks of all compositions are currently known, of which about 50 are pure silica materials. This is known as the zeolite conundrum--why have so few of all the possible structures been made? Several criteria have been formulated to explain why most zeolites are unfeasible synthesis targets. Here we demonstrate the synthesis of two such 'unfeasible' zeolites, IPC-9 and IPC-10, through the assembly-disassembly-organization-reassembly mechanism. These new high-silica zeolites have rare characteristics, such as windows that comprise odd-membered rings. Their synthesis opens up the possibility of preparing other zeolites that have not been accessible by traditional solvothermal synthetic methods. We envisage that these findings may lead to a step change in the number and types of zeolites available for future applications.
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              ITQ-15: the first ultralarge pore zeolite with a bi-directional pore system formed by intersecting 14- and 12-ring channels, and its catalytic implications.

              The pore topology of ITQ-15 zeolite consists of an ultra-large 14-ring channel that is intersected perpendicularly by a 12-ring pore; acid sites have been introduced in its framework and this unique structure shows advantages over unidirectional ultralarge pore zeolites for diffusing and reacting large molecules.
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                Author and article information

                Journal
                J Am Chem Soc
                J. Am. Chem. Soc
                ja
                jacsat
                Journal of the American Chemical Society
                American Chemical Society
                0002-7863
                1520-5126
                20 February 2019
                13 March 2019
                : 141
                : 10
                : 4453-4459
                Affiliations
                []School of Chemistry and EaStCHEM, University of St. Andrews , North Haugh, St. Andrews, Fife KY16 9ST, United Kingdom
                []Department of Physical and Macromolecular Chemistry Faculty of Sciences, Charles University , Hlavova 8, 128 43 Prague 2, Czech Republic
                Author notes
                Article
                10.1021/jacs.9b00643
                6515985
                30786710
                97b43175-4830-41bd-90ee-0a43915ef913
                Copyright © 2019 American Chemical Society

                This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.

                History
                : 18 January 2019
                Categories
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                Custom metadata
                ja9b00643
                ja-2019-00643k

                Chemistry
                Chemistry

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