Establishing hierarchy

Establishing hierarchy: The chain of events leading to the formation of silicalite-1 nanosheets

Zhu, Xiaochun (Eindhoven University of Technology)
Goesten, M.G. (Eindhoven University of Technology)
Koekkoek, Arjan J J (Eindhoven University of Technology)
Mezari, Brahim (Eindhoven University of Technology)
Kosinov, Nikolay (Eindhoven University of Technology)
Filonenko, Georgy (Eindhoven University of Technology)
Friedrich, Heiner (Eindhoven University of Technology)
Rohling, Roderigh (Eindhoven University of Technology)
Szyja, Bartłomiej M. (Eindhoven University of Technology)
Gascon, Jorge (TU Delft ChemE/Catalysis Engineering)
Kapteijn, F. (TU Delft ChemE/Catalysis Engineering)
Hensen, Emiel J M (Eindhoven University of Technology)

2016

In applying a multi-scale spectroscopic and computational approach, we demonstrate that the synthesis of stacked zeolite silicalite-1 nanosheets, in the presence of a long-tail diquaternary ammonium salt surfactant, proceeds through a pre-organised phase in the condensed state. In situ small-angle X-ray scattering, coupled to paracrystalline theory, and backed by electron microscopy, shows that this phase establishes its meso-scale order within the first five hours of hydrothermal synthesis. Quasi in situ vibrational and solid-state NMR spectroscopy reveal that this meso-shaped architecture already contains some elementary zeolitic features. The key to this coupled organisation at both micro- and meso-scale, is a structure-directing agent that is ambifunctional in shaping silica at the meso-scale whilst involved in molecular recognition at the micro-scale. The latter feature is particularly important and requires the structure-directing agent to reside within the silica matrix already at early stages of the synthesis. From here, molecular recognition directs stabilization of precursor species and their specific embedding into a lattice, as shown by force-field molecular dynamics calculations. These calculations, in line with experiment, further show how it is possible to subtly tune both the zeolite topology and aspect ratio of the condensating crystals, by modifying the headgroup of the structure-directing agent.

http://resolver.tudelft.nl/uuid:844f69d8-9408-484f-b93f-e233728ecec1

https://doi.org/10.1039/c6sc01295g

2041-6520

Chemical Science, 7 (10), 6506-6513

Institutional Repository

journal article

© 2016 Xiaochun Zhu, M.G. Goesten, Arjan J J Koekkoek, Brahim Mezari, Nikolay Kosinov, Georgy Filonenko, Heiner Friedrich, Roderigh Rohling, Bartłomiej M. Szyja, Jorge Gascon, F. Kapteijn, Emiel J M Hensen