Low-temperature binding of NO adsorbed on MIL-100(Al)-A case study for the application of high resolution pulsed EPR methods and DFT calculations

Mendt M, Barth B, Hartmann M, Poeppl A (2017)

Publication Language: English

Publication Status: Published

Publication Type: Journal article, Original article

Publication year: 2017

Journal

Journal of Chemical Physics AIP Publishing

Publisher: AMER INST PHYSICS

Book Volume: 147

Journal Issue: 22

DOI: 10.1063/1.4995551

Abstract

The low-temperature binding of nitric oxide (NO) in the metal-organic framework MIL-100(Al) has been investigated by pulsed electron nuclear double resonance and hyperfine sublevel correlation spectroscopy. Three NO adsorption species have been identified. Among them, one species has been verified experimentally to bind directly to an Al-27 atom and all its relevant N-14 and Al-27 hyperfine interaction parameters have been determined spectroscopically. Those parameters fit well to the calculated ones of a theoretical cluster model, which was derived by density functional theory (DFT) in the present work and describes the low temperature binding of NO to the regular coordinatively unsaturated Al3+ site of the MIL-100(Al) structure. As a result, the Lewis acidity of that site has been characterized using the NO molecule as an electron paramagnetic resonance active probe. The DFT derived wave function analysis revealed a bent end-on coordination of the NO molecule adsorbed at that site which is almost purely ionic and has a weak binding energy. The calculated flat potential energy surface of this species indicates the ability of the NO molecule to freely rotate at intermediate temperatures while it is still binding to the Al3+ site. For the other two NO adsorption species, no structural models could be derived, but one of them is indicated to be adsorbed at the organic part of the metal-organic framework. Hyperfine interactions with protons, weakly coupled to the observed NO adsorption species, have also been measured by pulsed electron paramagnetic resonance and found to be consistent with their attribution to protons of the MIL-100(Al) benzenetricarboxylate ligand molecules. Published by AIP Publishing.

Authors with CRIS profile

Benjamin Barth Interdisziplinäres Zentrum Erlangen Catalysis Resource Center (ECRC) Martin Hartmann Professur für Katalyse

Additional Organisation(s)

Interdisziplinäres Zentrum Erlangen Catalysis Resource Center (ECRC) Exzellenz-Cluster Engineering of Advanced Materials

Involved external institutions

Universität Leipzig DE Germany (DE)

How to cite

APA:

Mendt, M., Barth, B., Hartmann, M., & Poeppl, A. (2017). Low-temperature binding of NO adsorbed on MIL-100(Al)-A case study for the application of high resolution pulsed EPR methods and DFT calculations. Journal of Chemical Physics, 147(22). https://dx.doi.org/10.1063/1.4995551

MLA:

Mendt, Matthias, et al. "Low-temperature binding of NO adsorbed on MIL-100(Al)-A case study for the application of high resolution pulsed EPR methods and DFT calculations." Journal of Chemical Physics 147.22 (2017).

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