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Structural Deterioration of Well‐Faceted MOFs upon H 2 S Exposure and Its Effect in the Adsorption Performance
Author(s) -
Reljic Snezana,
BrotoRibas Anna,
CuadradoCollados Carlos,
Jardim Erika O.,
Maspoch Daniel,
Imaz Inhar,
SilvestreAlbero Joaquin
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202002473
Subject(s) - adsorption , materials science , crystallography , mesoporous material , octahedron , diffraction , metal , metal organic framework , chemical engineering , nanotechnology , chemical physics , chemistry , crystal structure , metallurgy , organic chemistry , optics , catalysis , physics , engineering
The structural deterioration of archetypical, well‐faceted metal–organic frameworks (MOFs) has been evaluated upon exposure to an acidic environment (H 2 S). Experimental results show that the structural damage highly depends on the nature of the hybrid network (e.g., softness of the metal ions, hydrophilic properties, among others) and the crystallographic orientation of the exposed facets. Microscopy images show that HKUST‐1 with well‐defined octahedral (111) facets is completely deteriorated, ZIF‐8 with preferentially exposed (110) facets exhibits a large external deterioration with the development of holes or cavities in the mesoporous range, whereas UiO‐66‐NH 2 with (111) exposed facets, and PCN‐250 with (100) facets does not reflect any sign of surface damage. Despite the selectivity in the external deterioration, X‐ray diffraction and gas adsorption measurements confirm that indeed all MOFs suffer an important internal deterioration, these effects being more severe for MOFs based on softer cations (e.g., Cu‐based HKUST‐1 and Fe‐based PCN‐250). These structural changes have inevitable important effects in the final adsorption performance for CO 2 and CH 4 at low and high pressures.