Evidence for a chemical clock in oscillatory formation of UiO-66.
Chemical clocks are often used as exciting classroom experiments, where an induction time is followed by rapidly changing colours that expose oscillating concentration patterns. This type of reaction belongs to a class of nonlinear chemical kinetics also linked to chaos, wave propagation and Turing patterns. Despite its vastness in occurrence and applicability, the clock reaction is only well understood for liquid-state processes. Here we report a chemical clock reaction, in which a solidifying entity, metal-organic framework UiO-66, displays oscillations in crystal dimension and number, as shown by X-ray scattering. In rationalizing this result, we introduce a computational approach, the metal-organic molecular orbital methodology, to pinpoint interaction between the tectonic building blocks that construct the metal-organic framework material. In this way, we show that hydrochloric acid plays the role of autocatalyst, bridging separate processes of condensation and crystallization.
Catalysis Engineering, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands.|Inorganic Materials Chemistry, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands.
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Goesten
Catalysis Engineering, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands.
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de Lange
Catalysis Engineering, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands.
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Olivos-Suarez
Catalysis Engineering, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands.
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Bavykina
Radiation Science and Technology, Mekelweg 15, 2629 JB Delft, The Netherlands.
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Serra-Crespo
National Synchrotron Light Source, Brookhaven National Laboratory, Upton, New York 11973, USA.|Helmholtz-Zentrum Geesthacht, D-21502 Geesthacht, Germany.
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Krywka
Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling (ACMM), VU University, de Boelelaan 1083, 1081 HV Amsterdam, The Netherlands.|Institute of Molecules and Materials (IMM), Radboud University, Heyendaalseweg 135, 6525 AJ Nijmegen, The Netherlands.
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Bickelhaupt
Catalysis Engineering, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands.
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Kapteijn
Catalysis Engineering, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands.
Jorge
0000-0001-7558-7123
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Gascon