Center for Molecular Modeling - H. Depauw

Elucidating the Vibrational Fingerprint of the Flexible Metal-Organic Framework MIL-53(Al) Using a Combined Experimental/Computational Approach

alexander — Wed, 08 Nov 2017 12:46:42 +0000

A.E.J. Hoffman, L. Vanduyfhuys, I. Nevjestic, J. Wieme, S.M.J. Rogge, H. Depauw, P. Van der Voort, H. Vrielinck, V. Van Speybroeck

Journal of Physical Chemistry C

122, 5, 2734-2746

2018

Abstract

In this work mid-infrared (mid-IR), far-IR, and Raman spectra are presented for the distinct (meta)stable phases of the flexible metal-organic framework MIL-53(Al). Static density functional theory (DFT) simulations are performed allowing for the identification of all IR active modes, which is unprecedented in the low-frequency region. A unique vibrational fingerprint is revealed, resulting from aluminum-oxide backbone stretching modes, which can be used to clearly distinguish the IR spectra of the closed- and large-pore phases. Furthermore, molecular dynamics simulations based on a DFT description of the potential energy surface enable to determine the theoretical Raman spectrum of the closed- and large-pore phases for the first time. An excellent correspondence between theory and experiment is observed. Both the low-frequency IR and Raman spectra show major differences in vibrational modes between the closed- and large-pore phases indicating changes in lattice dynamics between the two structures. In addition, several collective modes related to the breathing mechanism in MIL-53(Al) are identified. In particular, we rationalize the importance of the trampoline-like motion of the linker for the phase transition.

Open Access version available at UGent repository

Gold Open Access

DOI

http://dx.doi.org/10.1021/acs.jpcc.7b11031

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published.pdf

A series of sulfonic acid functionalized mixed-linker DUT-4 analogues: synthesis, gas sorption properties and catalytic performance

kevin — Fri, 28 Jul 2017 15:08:18 +0000

G. Wang, K. Leus, K. Hendrickx, J. Wieme, H. Depauw, Y-Y Liu, V. Van Speybroeck, P. Van der Voort

Dalton Transactions

46, 14356

2017

Abstract

In this work, we present the successful synthesis of a series of sulfonic acid functionalized mixed-linker metal–organic frameworks (MOFs) having the DUT-4 topology by using different ratios of 2,6-naphthalenedicarboxylic acid (H2-NDC) and 4,8-disulfonaphthalene-2,6-dicarboxylic acid (H2-NDC-2SO3H) in one-pot reactions. The obtained materials were fully characterized and their CO2 adsorption properties at low and high pressures were studied and compared with those of the pristine DUT-4 material. Generally, the CO2 adsorption capacities range from 3.28 and 1.36 mmol g−1 for DUT-4 to 1.54 and 0.78 mmol g−1 for DUT-4-SO3H (50) up to 1 bar at 273 K and 303 K, respectively. Computational calculations corroborated the structural changes of the material in function of the loading of sulfonic acid groups. Furthermore, due to the strong Brønsted acid character, the resulting sulfonic acid based MOF material was evaluated as a catalyst for the ring opening of styrene oxide with methanol as a nucleophile under mild conditions, showing almost full conversion (99%) after 5 hours of reaction. A hot filtration experiment demonstrated that the catalysis occurred heterogeneously and the catalyst could be recovered and reused for multiple runs without significant loss in activity and crystallinity.

DOI

http://dx.doi.org/10.1039/C7DT02752D

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10.1039@C7DT02752D.pdf

Systematic study of the chemical and hydrothermal stability of selected "stable" Metal Organic Frameworks

kevin — Thu, 24 Sep 2015 15:25:30 +0000

K. Leus, T. Bogaerts, J. De Decker, H. Depauw, K. Hendrickx, H. Vrielinck, V. Van Speybroeck, P. Van der Voort

Microporous and Mesoporous Materials

226, 110-116

2016

Abstract

In this work, the hydrothermal and chemical stability towards acids, bases, air, water and peroxides of Metal Organic Frameworks, that are commonly considered to be stable, is presented. As a proof of stability both the crystallinity and porosity are measured before and after exposure to the stress test. The major part of the MOFs examined in this study showed a good hydrothermal stability except for the UiO-67, NH2-MIL-101 (Al) and CuBTC material. The chemical stability towards acids and bases show a similar tendency and an ordering can be proposed as: MIL-101(Cr)>NH2-UiO-66>UiO-66>UiO-67>NH2-MIL-53>MIL-53(Al)>ZIF-8>CuBTC>NH2-MIL-101(Al). In the tests with the H2O2 solution most materials behaved poorly, only the UiO-66 and NH2-UiO-66 framework showed a good stability.

DOI

http://dx.doi.org/10.1016/j.micromeso.2015.11.055

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2016 - Leus - MMM - 226 - 110-116.pdf

Understanding the breathing behavior of the flexible metal-organic framework MIL-53(Al) using computational vibrational spectroscopy

alexander — Mon, 06 May 2019 08:03:24 +0000

A.E.J. Hoffman, L. Vanduyfhuys, I. Nevjestic, J. Wieme, S.M.J. Rogge, H. Depauw, P. Van der Voort, H. Vrielinck, V. Van Speybroeck

ISBN/ISSN:

Poster

Conference / event / venue

MOFSIM2019

Ghent, Belgium

Wednesday, 10 April, 2019 to Friday, 12 April, 2019

Understanding the breathing behavior of the flexible metal-organic framework MIL-53(Al) using computational vibrational spectroscopy

alexander — Mon, 06 May 2019 08:01:02 +0000

A.E.J. Hoffman, L. Vanduyfhuys, I. Nevjestic, J. Wieme, S.M.J. Rogge, H. Depauw, P. Van der Voort, H. Vrielinck, V. Van Speybroeck

ISBN/ISSN:

Poster

Conference / event / venue

Computational spectroscopy: bridging theory and experiment

Como, Italy

Sunday, 9 September, 2018 to Friday, 14 September, 2018

Understanding the breathing behavior of the flexible metal-organic framework MIL-53(Al) using computational vibrational spectroscopy

alexander — Mon, 06 May 2019 07:58:10 +0000

A.E.J. Hoffman, L. Vanduyfhuys, I. Nevjestic, J. Wieme, S.M.J. Rogge, H. Depauw, P. Van der Voort, H. Vrielinck, V. Van Speybroeck

ISBN/ISSN:

Poster

Conference / event / venue

Ab initio modeling in solid state chemistry

Torino, Italy

Sunday, 2 September, 2018 to Friday, 7 September, 2018

Elucidating the Vibrational Fingerprint of the Flexible Metal-Organic Framework MIL-53(Al) Using a Combined Experimental/Computational Approach

jelle — Sun, 29 Oct 2017 21:46:37 +0000

A.E.J. Hoffman, L. Vanduyfhuys, I. Nevjestic, J. Wieme, S.M.J. Rogge, H. Depauw, P. Van der Voort, H. Vrielinck, V. Van Speybroeck

ISBN/ISSN:

Poster

Conference / event / venue

EUROMOF 2017

Delft, The Netherlands

Monday, 30 October, 2017