Deciphering the Mechanism of Crystallization of UiO-66 Metal-Organic Framework.

Autor: Semivrazhskaya OO; Laboratory for Organic Chemistry, ETH Zurich, Vladimir-Prelog-Weg 3, 8093, Zurich, Switzerland., Salionov D; Bioenergy and Catalysis Laboratory, Paul Scherrer Institute, 5232, Villigen PSI, Switzerland., Clark AH; Operando Spectroscopy Group, Paul Scherrer Institute, 5232, Villigen PSI, Switzerland., Casati NPM; Laboratory for Synchrotron Radiation-Condensed Matter, Paul Scherrer Institute, 5232, Villigen PSI, Switzerland., Nachtegaal M; Operando Spectroscopy Group, Paul Scherrer Institute, 5232, Villigen PSI, Switzerland., Ranocchiari M; Laboratory for Catalysis and Sustainable Chemistry, Paul Scherrer Institute, 5232, Villigen PSI, Switzerland., Bjelić S; Bioenergy and Catalysis Laboratory, Paul Scherrer Institute, 5232, Villigen PSI, Switzerland., Verel R; Institute for Chemistry and Bioengineering, ETH Zurich, Vladimir-Prelog-Weg 1, 8093, Zurich, Switzerland., van Bokhoven JA; Laboratory for Catalysis and Sustainable Chemistry, Paul Scherrer Institute, 5232, Villigen PSI, Switzerland.; Institute for Chemistry and Bioengineering, ETH Zurich, Vladimir-Prelog-Weg 1, 8093, Zurich, Switzerland., Sushkevich VL; Laboratory for Catalysis and Sustainable Chemistry, Paul Scherrer Institute, 5232, Villigen PSI, Switzerland.
Jazyk: angličtina
Zdroj: Small (Weinheim an der Bergstrasse, Germany) [Small] 2023 Dec; Vol. 19 (52), pp. e2305771. Date of Electronic Publication: 2023 Aug 27.
DOI: 10.1002/smll.202305771
Abstrakt: Zirconium-containing metal-organic framework (MOF) with UiO-66 topology is an extremely versatile material, which finds applications beyond gas separation and catalysis. However, after more than 10 years after the first reports introducing this MOF, understanding of the molecular-level mechanism of its nucleation and growth is still lacking. By means of in situ time-resolved high-resolution mass spectrometry, Zr K-edge X-ray absorption spectroscopy, magic-angle spinning nuclear magnetic resonance spectroscopy, and X-ray diffraction it is showed that the nucleation of UiO-66 occurs via a solution-mediated hydrolysis of zirconium chloroterephthalates, whose formation appears to be autocatalytic. Zirconium-oxo nodes form directly and rapidly during the synthesis, the formation of pre-formed clusters and stable non-stoichiometric intermediates are not observed. The nuclei of UiO-66 possess identical to the crystals local environment, however, they lack long-range order, which is gained during the crystallization. Crystal growth is the rate-determining step, while fast nucleation controls the formation of the small crystals of UiO-66 with a narrow size distribution of about 200 nanometers.
(© 2023 The Authors. Small published by Wiley-VCH GmbH.)
Databáze: MEDLINE
Externí odkaz: