Abstract
High-silica zeolites, some of the most important and widely used catalysts in industry, have potential for application across a wide range of traditional and emerging technologies. The many structural topologies of zeolites have a variety of potential uses, so a strong drive to create new zeolites exists. Here, we present a protocol, the assembly–disassembly–organization–reassembly (ADOR) process, for a relatively new method of preparing these important solids. It allows the synthesis of new high-silica zeolites (Si/Al >1,000), whose synthesis is considered infeasible with traditional (solvothermal) methods, offering new topologies that may find novel applications. We show how to identify the optimal conditions (e.g., duration of reaction, temperature, acidity) for ADOR, which is a complex process with different possible outcomes. Following the protocol will allow researchers to identify the different products that are possible from a reaction without recourse to repetitive and time-consuming trial and error. In developing the protocol, germanium-containing UTL zeolites were subjected to hydrolysis conditions using both water and hydrochloric acid as media, which provides an understanding of the effects of temperature and pH on the disassembly (D) and organization (O) steps of the process that define the potential products. Samples were taken from the ongoing reaction periodically over a minimum of 8 h, and each sample was analyzed using powder X-ray diffraction to yield a time course for the reaction at each set of conditions; selected samples were analyzed using transmission electron microscopy and solid-state NMR spectroscopy.
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Data supporting this publication are available from the corresponding author upon request.
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Acknowledgements
The authors thank the EPSRC (grants: EP/K025112/1, EP/K005499/1, EP/K503162/1, EP/N509759/1) for funding. R.E.M., J.C. and M.M. acknowledge OP VVV ‘Excellent Research Teams’, project no. CZ.02.1.01/0.0/0.0/15_003/0000417-CUCAM. S.E.A. thanks the Royal Society and the Wolfson Foundation for a merit award. J.C. acknowledges the Czech Science Foundation (P106/12/G015). We thank O. Morris for the animation of the process that is available as Supplementary Video 1.
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S.E.H. completed the development of the protocol and collected the synthesis data. M.M. completed the electron microscopy; and C.M.R., G.P.M.B. and S.E.A. collected the solid-state NMR data. P.S.W., J.Č. and R.E.M. initiated the project. All authors checked the protocol and contributed to the writing of the paper.
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Key references using this protocol
Mazur, M. et al. Nat. Chem. 8, 58–62 (2015): https://www.nature.com/articles/nchem.2374
Wheatley, P. S. et al. Angew. Chem. Int. Ed. 53, 13210–13214 (2014): https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.201407676
Roth, W. J. et al. Nat. Chem. 5, 628–633 (2013): https://www.nature.com/articles/nchem.1662
Eliášová, P. et al. Chem. Soc. Rev. 44, 7177–7206 (2015): https://pubs.rsc.org/-/content/articlepdf/2015/cs/c5cs00045a?page=search
Integrated supplementary information
Supplementary Figure 1 1H MAS NMR spectra (9.4 T, 10 kHz MAS) showing the changes in 1H environments in Ge-UTL occurring during hydrolysis at 100 °C in water.
3 p.p.m. – Sharp peak from non-coordinated water; 4-10 p.p.m. - Unresolved hydroxyls. No proton signals other than minimal probe background is observed for calcined Ge-UTL.
Supplementary Figure 2 1H MAS NMR spectra (9.4 T, 10 kHz MAS) showing the different proton environments in hydrolyzed Ge-UTL (5 min; water; 18 °C), utilizing different drying methods.
Drying in the oven was chosen for this study as it produces a relatively dry sample (compared to air drying) suitable for PXRD collection and NMR acquisition, with confirmed presence of hydroxyls. Although the samples produced via vacuum drying and argon loading are drier, due to the high-throughput nature of the PXRD area of this study, oven drying, which takes only 10 minutes, was deemed the most suitable method to proceed with. All reactions involved hydrolyzing 50 mg of calcined Ge-UTL in 50 mg of distilled water. Air drying was carried out at 18 °C for 10 minutes, with oven drying taking place at 110 °C for the same amount of time. Vacuum drying was carried out using Schlenk apparatus at 110 °C overnight to give a vacuum approaching 10–5 Torr. Samples dried in this manner were cooled to room temperature, flushed with argon and then flame sealed under argon. Spectra are scaled according to proton peak intensity (Vacuum: Oven: Air = 1: 2.7: 8.7).
Supplementary Figure 3 TEM images of the samples of Ge-UTL hydrolyzed in water at 100 °C.
a = Parent Ge-UTL; b = after 1 min; c = after 1 hr; d = after 4 hr. FFT images are shown as insets. d spacings can be measured using standard software.
Supplementary information
Supplementary Text and Figures
Supplementary Figures 1–3 and Supplementary Table 1
Supplementary Video 1
ADOR protocol video: animation of the ADOR protocol.
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Henkelis, S.E., Mazur, M., Rice, C.M. et al. A procedure for identifying possible products in the assembly–disassembly–organization–reassembly (ADOR) synthesis of zeolites. Nat Protoc 14, 781–794 (2019). https://doi.org/10.1038/s41596-018-0114-6
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DOI: https://doi.org/10.1038/s41596-018-0114-6
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