Metal-organic framework (MOF) crystallization is governed by molecular assembly processes in the pre-nucleation stage. Yet, unravelling these pre-nucleation pathways and rationalizing their impact on crystal formation poses a great challenge since probing molecular-scale assemblies and macroscopic particles simultaneously is very complex. Herein, we present a multimodal, integrated approach to monitor MOF nucleation across multiple length scales by combining in situ optical spectroscopy, mass spectrometry, and molecular simulations. This approach allows tracing initial metal-organic complexes in solution and their assembly into oligomeric nuclei and simultaneously probing particle formation. During Co-ZIF-67 nucleation, a metal-organic pool forms with a variety of complexes caused by ligand exchange and symmetry reduction reactions. We discriminate complexes capable of initiating nucleation from growth species required for oligomerization into frameworks. Co4-nuclei are observed, which grow into particles following autocatalytic kinetics. The geometric and compositional variability of metal-organic pool species clarifies long-debated amorphous zeolitic imidazolate framework (ZIF)-particle nucleation and non-classic pathways of MOF crystallization.

Elucidation of the pre-nucleation phase directing metal-organic framework formation / Filez, M.; Caratelli, C.; Rivera-Torrente, M.; Muniz Miranda, F.; Hoek, M.; Altelaar, M.; Heck, A. J. R.; Van Speybroeck, V.; Weckhuysen, B. M.. - In: CELL REPORTS PHYSICAL SCIENCE. - ISSN 2666-3864. - 2:12(2021), pp. 100680-100696. [10.1016/j.xcrp.2021.100680]

Elucidation of the pre-nucleation phase directing metal-organic framework formation

Muniz Miranda F.;
2021-01-01

Abstract

Metal-organic framework (MOF) crystallization is governed by molecular assembly processes in the pre-nucleation stage. Yet, unravelling these pre-nucleation pathways and rationalizing their impact on crystal formation poses a great challenge since probing molecular-scale assemblies and macroscopic particles simultaneously is very complex. Herein, we present a multimodal, integrated approach to monitor MOF nucleation across multiple length scales by combining in situ optical spectroscopy, mass spectrometry, and molecular simulations. This approach allows tracing initial metal-organic complexes in solution and their assembly into oligomeric nuclei and simultaneously probing particle formation. During Co-ZIF-67 nucleation, a metal-organic pool forms with a variety of complexes caused by ligand exchange and symmetry reduction reactions. We discriminate complexes capable of initiating nucleation from growth species required for oligomerization into frameworks. Co4-nuclei are observed, which grow into particles following autocatalytic kinetics. The geometric and compositional variability of metal-organic pool species clarifies long-debated amorphous zeolitic imidazolate framework (ZIF)-particle nucleation and non-classic pathways of MOF crystallization.
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12
100680
100696
Elucidation of the pre-nucleation phase directing metal-organic framework formation / Filez, M.; Caratelli, C.; Rivera-Torrente, M.; Muniz Miranda, F.; Hoek, M.; Altelaar, M.; Heck, A. J. R.; Van Speybroeck, V.; Weckhuysen, B. M.. - In: CELL REPORTS PHYSICAL SCIENCE. - ISSN 2666-3864. - 2:12(2021), pp. 100680-100696. [10.1016/j.xcrp.2021.100680]
Filez, M.; Caratelli, C.; Rivera-Torrente, M.; Muniz Miranda, F.; Hoek, M.; Altelaar, M.; Heck, A. J. R.; Van Speybroeck, V.; Weckhuysen, B. M.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11380/1258577
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