Controlling the molecular diffusion in MOFs with the acidity of monocarboxylate modulators

The catalytic performance of metal-organic frameworks (MOFs) is related to their physicochemical properties, such as particle size, defect chemistry and porosity, which can be potentially controlled by coordination modulation. By combining PXRD, 1 HNMR, FT-IR, and N 2 uptake measurements we have gai...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2021-08, Vol.5 (32), p.11291-11299
Main Authors: Lázaro, Isabel Abánades, Popescu, Catalin, Cirujano, Francisco G
Format: Article
Language:English
Subjects:
Amines
Catalytic activity
Clusters
Defects
Material properties
Metal-organic frameworks
Modulators
Molecular diffusion
NMR
Nuclear magnetic resonance
Polydispersity
Porosity
Ring opening
Spatial distribution
Water stability
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Summary:The catalytic performance of metal-organic frameworks (MOFs) is related to their physicochemical properties, such as particle size, defect chemistry and porosity, which can be potentially controlled by coordination modulation. By combining PXRD, 1 HNMR, FT-IR, and N 2 uptake measurements we have gained insights into the control of different types of defects (missing linker or missing cluster consequence of the spatial distribution of missing linkers, and a combination of both) by the type of modulator employed. We show that the molar percent of defects, either as missing linkers or as a part of missing cluster defects, is related to the acidity of a modulator and its subsequent incorporation into the UiO-66 structure. Modulators with strong acidity and small size result in a considerable defect induction that causes an increase in the external surface area and mesopore volume, which is beneficial for the ring-opening of epoxides with amines, using UiO-66 defect-modulated MOFs as heterogeneous catalysts. The catalytic performance of metal-organic frameworks (MOFs) is related to their physicochemical properties, such as particle size, defect chemistry and porosity, and their control can be potentially achieved by coordination modulation.
ISSN:1477-9226
1477-9234
DOI:10.1039/d1dt01773j