Impact of Small Adsorbates in the Vibrational Spectra of Mg- and Zn-MOF-74 Revealed by First-Principles Calculations

Romero-Muniz, Carlos, Gavira-Vallejo, José María, Merkling, Patrick y Calero, Sofía . (2020) Impact of Small Adsorbates in the Vibrational Spectra of Mg- and Zn-MOF-74 Revealed by First-Principles Calculations. ACS Applied Materials & Interfaces

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Título Impact of Small Adsorbates in the Vibrational Spectra of Mg- and Zn-MOF-74 Revealed by First-Principles Calculations
Autor(es) Romero-Muniz, Carlos
Gavira-Vallejo, José María
Merkling, Patrick
Calero, Sofía
Materia(s) Física
Abstract In this work, we analyze the influence of small adsorbates on the vibrational spectra of Mg- and Zn-metal–organic framework MOF-74 by means of first-principles calculations. In particular, we consider the adsorption of four representative species of different interaction strengths: Ar, CO2, H2O, and NH3. Apart from a comprehensive characterization of the structural and energetic aspects of empty and loaded MOFs, we use a fully quantum ab initio approach to evaluate the Raman and IR activities of the normal modes, leading to the construction of the whole vibrational spectra. Under this approach, not only are we able to proceed with the complete assignment of the spectra in terms of the usual internal coordinates but also we can discern the most relevant vibrational fingerprints of the adsorbates and their impact on the whole MOF spectra. On the one hand, some of the typical vibrational modes of the small molecules are slightly shifted but still visible when adsorbed on the MOFs, especially those appearing at high wavenumbers where the empty MOFs lack IR/Raman signals. On the other hand, some bands arising from the organic ligands are affected by the presence of the absorbates, displaying non-negligible frequency shifts, in agreement with recent experiments. We find a strong correlation between all of these frequency shifts and the interaction strength of the adsorbate with the hosting framework. The findings presented in this work expand the capabilities of vibrational spectroscopy techniques to analyze porous materials and can be useful for the design of sensors and new devices based on MOF technology.
Palabras clave metal−organic framework
MOF-74
vibrational spectroscopy
density functional theory
gas adsorption
Editor(es) American Chemical Society
Fecha 2020
Formato application/pdf
Identificador bibliuned:DptoCTFQ-FCIE-Articulos-Jmgavira-0005
http://e-spacio.uned.es/fez/view/bibliuned:DptoCTFQ-FCIE-Articulos-Jmgavira-0005
DOI - identifier 10.1021/acsami.0c16629
ISSN - identifier 1944-8252
Nombre de la revista ACS Applied Materials & Interfaces
Publicado en la Revista ACS Applied Materials & Interfaces
Idioma eng
Versión de la publicación acceptedVersion
Tipo de recurso Article
Derechos de acceso y licencia http://creativecommons.org/licenses/by-nc-nd/4.0
info:eu-repo/semantics/openAccess
Tipo de acceso Acceso abierto
Notas adicionales The registered version of this article, first published in ACS Applied Materials & Interfaces, is available online at the publisher's website: American Chemical Society, https://doi.org/10.1021/acsami.0c16629

 
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Creado: Fri, 02 Feb 2024, 22:54:48 CET