Synthesis, isotopic enrichment and solid-state NMR characterization of zeolites derived from the assembly, disassembly, organisation, reassembly process
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The great utility and importance of zeolites in fields as diverse as industrial catalysis and medicine has driven considerable interest in the ability to target new framework types with novel properties and applications. The recently introduced and unconventional assembly, disassembly, organization, reassembly (ADOR) method represents one exciting new approach to obtain solids with targeted structures by selectively disassembling preprepared hydrolytically unstable frameworks and then reassembling the resulting products to form materials with new topologies. However, the hydrolytic mechanisms underlying such a powerful synthetic method are not understood in detail, requiring further investigation of the kinetic behavior and the outcome of reactions under differing conditions. In this work, we report the optimized ADOR synthesis, and subsequent solid-state characterization, of 17O- and doubly 17O- and 29Si-enriched UTL-derived zeolites, by synthesis of 29Si-enriched starting Ge-UTL frameworks and incorporation of 17O from 17O-enriched water during hydrolysis. 17O and 29Si NMR experiments are able to demonstrate that the hydrolysis and rearrangement process occurs over a much longer time scale than seen by diffraction. The observation of unexpectedly high levels of 17O in the bulk zeolitic layers, rather than being confined only to the interlayer spacing, reveals a much more extensive hydrolytic rearrangement than previously thought. This work sheds new light on the role played by water in the ADOR process and provides insight into the detailed mechanism of the structural changes involved.
Bignami , G P M , Dawson , D M , Seymour , V R , Wheatley , P S , Morris , R E & Ashbrook , S E M 2017 , ' Synthesis, isotopic enrichment and solid-state NMR characterization of zeolites derived from the assembly, disassembly, organisation, reassembly process ' Journal of the American Chemical Society , vol 139 , no. 14 , pp. 5140-5148 . DOI: 10.1021/jacs.7b00386
Journal of the American Chemical Society
© 2017 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.
We would like to thank the ERC (EU FP7 Consolidator Grant 614290 “EXONMR”), the Leverhulme Trust (IN-2012-094), and EPSRC (EP/K025112/1, EP/L014475/1, and EP/M506631/1 (for GPMB)). S.E.A. would like to thank the Royal Society and the Wolfson Foundation for a merit award. The research data (and/or materials) supporting this publication can be accessed at DOI: 10.17630/d66d1146-5892-4f14-8e41-dfc075a8cd91.
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