In situ solid-state NMR and XRD studies of the ADOR process and the unusual structure of zeolite IPC-6

Abstract

The assembly–disassembly–organization–reassembly (ADOR) mechanism is a recent method for preparing inorganic framework materials and, in particular, zeolites. This flexible approach has enabled the synthesis of isoreticular families of zeolites with unprecedented continuous control over porosity, and the design and preparation of materials that would have been difficult—or even impossible—to obtain using traditional hydrothermal techniques. Applying the ADOR process to a parent zeolite with the UTL framework topology, for example, has led to six previously unknown zeolites (named IPC-n, where n = 2, 4, 6, 7, 9 and 10). To realize the full potential of the ADOR method, however, a further understanding of the complex mechanism at play is needed. Here, we probe the disassembly, organization and reassembly steps of the ADOR process through a combination of in situ solid-state NMR spectroscopy and powder X-ray diffraction experiments. We further use the insight gained to explain the formation of the unusual structure of zeolite IPC-6.

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Figure 1: In situ NMR studies of the disassembly and organization (rearrangement) steps in the ADOR process.
Figure 2: The mechanism of the ADOR process as revealed by the in situ studies.
Figure 3: In situ XRD studies of the reassembly step of the ADOR process.
Figure 4: Experimental and simulated XRD patterns and the structure of IPC-6.
Figure 5: The possibilities for sequential rearrangement and reconnection of layers during the ADOR process.

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Acknowledgements

R.E.M. and M.N. thank the Royal Society and the Engineering and Physical Sciences Research Council (EPSRC) (Grants EP/L014475/1, EP/K025112/1 and EP/K005499/1) for funding work in this area. R.E.M. and J.Č. acknowledge the Czech Science Foundation for the project, P106/12/G015 and OP VVV “Excellent Research Teams”, project no. CZ.02.1.01/0.0/0.0/15_003/0000417, CUCAM. S.E.A. would like to thank the European Research Council (EU FP7 Consolidator Grant 614290 “EXONMR”) and the Royal Society and Wolfson Foundation for a merit award. We thank C. Tang for his assistance with the synchrotron PXRD work carried out at the Diamond Light Source, UK. The UK 850 MHz solid-state NMR Facility used in this research was funded by EPSRC and BBSRC (contract reference PR140003), as well as the University of Warwick including via part funding through Birmingham Science City Advanced Materials Projects 1 and 2 supported by Advantage West Midlands (AWM) and the European Regional Development Fund (ERDF). Collaborative assistance from the 850 MHz facility manager (D. Iuga, University of Warwick) is acknowledged. W.A.S. and D.S.W. acknowledge the Research Council of Norway for providing the computer time at the Norwegian supercomputer facilities (under the project number NN2875k).

Author information

P.S.W. designed the route and synthesized the enriched UTL samples. S.A.M., P.S.W. and D.S.F. completed the in situ PXRD. Y.T. and M.N. completed the initial ADOR synthesis. W.A.S. and D.S.W. simulated the PXRD using computational approaches. G.P.M.B., D.M.D. and S.E.A. designed and completed the NMR experiments. J.Č. collaborated on the design of the project, and R.E.M. and S.E.A coordinated the project and wrote the paper.

Correspondence to Russell E. Morris or Sharon E. Ashbrook.

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Morris, S., Bignami, G., Tian, Y. et al. In situ solid-state NMR and XRD studies of the ADOR process and the unusual structure of zeolite IPC-6. Nature Chem 9, 1012–1018 (2017). https://doi.org/10.1038/nchem.2761

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