Elucidating correlated defects in metal organic frameworks using theory-guided inelastic neutron scattering spectroscopy

Cavalcante, Lucas S. R.; Dettmann, Makena A.; Sours, Tyler; Yang, Dong; Daemen, Luke L.; Gates, Bruce C.; Kulkarni, Ambarish R.; Moulé, Adam J.

doi:10.1039/d2mh00914e

Elucidating correlated defects in metal organic frameworks using theory-guided inelastic neutron scattering spectroscopy

Journal Article · Mon Oct 31 00:00:00 UTC 2022 · Materials Horizons

DOI:https://doi.org/10.1039/d2mh00914e· OSTI ID:1924280

^[1]; ^[2]; Sours, Tyler ^[2]; ^[2]; Daemen, Luke L. ^[3]; ^[2]; Kulkarni, Ambarish R. ^[2]; ^[2]

Univ. of California, Davis, CA (United States); UC Davis
Univ. of California, Davis, CA (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Metal organic frameworks (MOFs) that incorporate metal oxide cluster nodes, exemplified by UiO-66, have been widely studied, especially in terms of their deviations from the ideal, defect-free crystalline structures. Although defects such as missing linkers, missing nodes, and the presence of adventitious synthesis-derived node ligands (such as acetates and formates) have been proposed, their exact structures remain unknown. Previously, it was demonstrated that defects are correlated and span multiple unit cells. The highly specialized techniques used in these studies are not easily applicable to other MOFs. Thus, there is a need to develop new experimental and computational approaches to understand the structure and properties of defects in a wider variety of MOFs. Here, we show how low-frequency phonon modes measured by inelastic neutron scattering (INS) spectroscopy can be combined with density functional theory (DFT) simulations to provide unprecedented insights into the defect structure of UiO-66. We are able to identify and assign peaks in the fingerprint region (<100 cm^–1) which correspond to phonon modes only present in certain defective topologies. Specifically, this analysis suggests that our sample of UiO-66 consists of predominantly defect-free fcu regions with smaller domains corresponding to a defective bcu topology with 4 and 2 acetate ligands bound to the Zr₆O₈ nodes. Importantly, the INS/DFT approach provides detailed structural insights (e.g., relative positions and numbers of acetate ligands) that are not accessible with microscopy-based techniques. Furthermore, the quantitative agreement between DFT simulations and the experimental INS spectrum combined with the relative simplicity of sample preparation, suggests that this methodology may become part of the standard and preferred protocol for the characterization of MOFs, and, in particular, for elucidating the structure defects in these materials.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of California, Davis, CA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; AC52-07NA27344; SC0010419; SC0012702

OSTI ID:: 1924280

Alternate ID(s):: OSTI ID: 1897313

Journal Information:: Materials Horizons, Journal Name: Materials Horizons Journal Issue: 1 Vol. 10; ISSN 2051-6347

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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