Elucidation of the pre-nucleation phase directing metal-organic framework formation
Filez, Matthias; Caratelli, Chiara; Rivera-Torrente, Miguel; Muniz-Miranda, Francesco; Hoek, Max; Altelaar, Maarten; Heck, Albert J.R.; Van Speybroeck, Veronique; Weckhuysen, Bert M.
(2021) Cell Reports Physical Science, volume 2, issue 12, pp. 1 - 16
(Article)
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
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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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Keywords: General Physics and Astronomy, General Materials Science, General Chemistry, General Energy, General Engineering
ISSN: 2666-3864
Publisher: Cell Press
Note: Funding Information: The authors acknowledge Dr. A.D. Chowdhury and Dr. Z. Ozturk for their valuable input and discussions. M.F. acknowledges the European Union's Horizon 2020 research and innovation program under the Marie Sklodowska-Curie grant agreement 748563. B.M.W. acknowledges funding from a European Research Council (ERC) Advanced Grant (321140) as well as the Netherlands Organization for Scientific Research (NWO) in the frame of a Gravitation Program MCEC (Netherlands Center for Multiscale Catalytic Energy Conversion, https://www.mcec-researchcenter.nl). C.C. F.M.-M. and V.V.S. acknowledge funding from the European Research Council under the ERC grant agreement 240483 and the European Union's Horizon 2020 research and innovation program (Consolidator ERC grant agreement 647755 ? DYNPOR) and the Research Board of the Ghent University. Computational resources and services were provided by the VSC (Flemish Supercomputer Center), funded by the Research Foundation Flanders (FWO) and the Flemish Government, department EWI. M.F. gratefully acknowledges his parents, wife, and children for their persistent support. M.F. and M.R.-T. prepared and characterized samples. M.F. performed VIS experiments. M.F. and M.H. performed ESI-MS experiments, supervised by A.J.R.H. M.F. performed data analysis of VIS and ESI-MS data and stochastic simulations. F.M.-M. performed static DFT, and C.C. performed MD and MTD simulations under supervision of V.V.S. M.F. and B.M.W. conceived the research idea and managed the project. All authors discussed the results and commented on the different versions of the manuscript. The authors declare no competing interests. Funding Information: The authors acknowledge Dr. A.D. Chowdhury and Dr. Z. Ozturk for their valuable input and discussions. M.F. acknowledges the European Union’s Horizon 2020 research and innovation program under the Marie Sklodowska-Curie grant agreement 748563 . B.M.W. acknowledges funding from a European Research Council (ERC) Advanced Grant ( 321140 ) as well as the Netherlands Organization for Scientific Research (NWO) in the frame of a Gravitation Program MCEC ( Netherlands Center for Multiscale Catalytic Energy Conversion , https://www.mcec-researchcenter.nl ). C.C., F.M.-M., and V.V.S. acknowledge funding from the European Research Council under the ERC grant agreement 240483 and the European Union’s Horizon 2020 research and innovation program (Consolidator ERC grant agreement 647755 – DYNPOR) and the Research Board of the Ghent University . Computational resources and services were provided by the VSC (Flemish Supercomputer Center), funded by the Research Foundation Flanders (FWO) and the Flemish Government, department EWI. M.F. gratefully acknowledges his parents, wife, and children for their persistent support. Publisher Copyright: © 2021 The Author(s)
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