Evidence for a chemical clock in oscillatory formation of UiO-66

被引:40
作者
Goesten, M. G. [1 ,2 ]
de lange, M. F. [1 ]
Olivos-Suarez, A. I. [1 ]
Bavykina, A. V. [1 ]
Serra-Crespo, P. [3 ]
Krywka, C. [4 ,5 ]
Bickelhaupt, F. M. [6 ,7 ,8 ]
Kapteijn, F. [1 ]
Gascon, Jorge [1 ]
机构
[1] Delft Univ Technol, Catalysis Engn, Julianalaan 136, NL-2628 BL Delft, Netherlands
[2] Eindhoven Univ Technol, Inorgan Mat Chem, POB 513, NL-5600 MB Eindhoven, Netherlands
[3] Radiat Sci & Technol, Mekelweg 15, NL-2629 JB Delft, Netherlands
[4] Brookhaven Natl Lab, Natl Synchrotron Light Source, Upton, NY 11973 USA
[5] Helmholtz Zentrum Geesthacht, D-21502 Geesthacht, Germany
[6] Vrije Univ Amsterdam, Dept Theoret Chem, de Boelelaan 1083, NL-1081 HV Amsterdam, Netherlands
[7] Vrije Univ Amsterdam, ACMM, de Boelelaan 1083, NL-1081 HV Amsterdam, Netherlands
[8] Radboud Univ Nijmegen, IMM, Heyendaalseweg 135, NL-6525 AJ Nijmegen, Netherlands
基金
欧洲研究理事会;
关键词
METAL-ORGANIC FRAMEWORK; ACTIVATION STRAIN MODEL; CORRELATION-ENERGY; APPROXIMATION; CRYSTALLIZATION; DIFFRACTION; CHEMISTRY;
D O I
10.1038/ncomms11832
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
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.
引用
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页数:8
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