Center for Molecular Modeling - J.-C. Tan

Quantum tunneling rotor as a sensitive atomistic probe of guests in a metal-organic framework

sven — Thu, 20 Jul 2023 12:32:21 +0000

K. Titov, M.R. Ryder, A. Lamaire, Z. Zeng, A.K. Chaudhari, J. Taylor, E.M. Mahdi, S.M.J. Rogge, S. Mukhopadhyay, S. Rudić, V. Van Speybroeck, F. Fernandez-Alonso, J.-C. Tan

Physical Review Materials

7, 073402

2023

Abstract

Quantum tunneling rotors in a zeolitic imidazolate framework ZIF-8 can provide insights into local gas adsorption sites and local dynamics of porous structure, which are inaccessible to standard physisorption or x-ray diffraction sensitive primarily to long-range order. Using in situ high-resolution inelastic neutron scattering at 3 K, we follow the evolution of methyl tunneling with respect to the number of dosed gas molecules. While nitrogen adsorption decreases the energy of the tunneling peak, and ultimately hinders it completely (0.33 meV to zero), argon substantially increases the energy to 0.42 meV. Ab initio calculations of the rotational barrier of ZIF-8 show an exception to the reported adsorption sites hierarchy, resulting in anomalous adsorption behavior and linker dynamics at subatmospheric pressure. The findings reveal quantum tunneling rotors in metal-organic frameworks as a sensitive atomistic probe of local physicochemical phenomena.

Gold Open Access

DOI

http://dx.doi.org/10.1103/PhysRevMaterials.7.073402

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PhysRevMaterials.7.073402.pdf

High-rate nanofluidic energy absorption in porous zeolitic frameworks

sven — Thu, 22 Apr 2021 19:37:50 +0000

Y. Sun, S.M.J. Rogge, A. Lamaire, S. Vandenbrande, J. Wieme, C.R. Siviour, V. Van Speybroeck, J.-C. Tan

Nature Materials

20 (7), 1015–1023

2021

Abstract

Optimal mechanical impact absorbers are reusable and exhibit high specific energy absorption. The forced intrusion of liquid water in hydrophobic nanoporous materials, such as zeolitic imidazolate frameworks (ZIFs), presents an attractive pathway to engineer such systems. However, to harness their full potential, it is crucial to understand the underlying water intrusion and extrusion mechanisms under realistic, high-rate deformation conditions. Here, we report a critical increase of the energy absorption capacity of confined water-ZIF systems at elevated strain rates. Starting from ZIF-8 as proof-of-concept, we demonstrate that this attractive rate dependence is generally applicable to cage-type ZIFs but disappears for channel-containing zeolites. Molecular simulations reveal that this phenomenon originates from the intrinsic nanosecond timescale needed for critical-sized water clusters to nucleate inside the nanocages, expediting water transport through the framework. Harnessing this fundamental understanding, design rules are formulated to construct effective, tailorable and reusable impact energy absorbers for challenging new applications.

DOI

http://dx.doi.org/10.1038/s41563-021-00977-6

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s41563-021-00977-6.pdf

Harder, better, faster, stronger: Designing hydrophobic cage-type materials as efficient high-rate shock absorbers

sven — Fri, 17 Sep 2021 09:07:33 +0000

S.M.J. Rogge, Y. Sun, A. Lamaire, S. Vandenbrande, J. Wieme, C.R. Siviour, J.-C. Tan, V. Van Speybroeck

ISBN/ISSN:

Talk

Conference / event / venue

EuroMOF2021

Online

Wednesday, 15 September, 2021

Conference reference

EuroMOF2021

ZIF-8 as a high-impact shock absorber? Unraveling the anomalous high-rate water intrusion in ZIF-8 by simulation and experiment

sven — Thu, 13 Jun 2019 10:44:32 +0000

S.M.J. Rogge, Y. Sun, A. Lamaire, S. Vandenbrande, J. Wieme, J.-C. Tan, V. Van Speybroeck

ISBN/ISSN:

Talk

Conference / event / venue

MMC

Oxford, United Kingdom

Tuesday, 18 June, 2019