Metal-organic frameworks (MOFs) emerged as adjustable and multipurpose
materials, which are now intensively investigated worldwide. They are composed of a
wide range of organic and inorganic building units which are a susceptible base for
various post-synthetic modifications (PSMs). In the last years, altering MOFs
composition has significantly contributed to their broad application in many fields,
especially in heterogeneous catalysis. PSMs are employed to improve the
physicochemical properties of MOFs such as stability or selectivity, but mostly to
generate catalytically active sites. Here, we report diverse methods of metal-
(exchange, doping, redox transformations) and ligand-based (functionalization,
exchange, installation, removal) PSMs of MOFs, which can be effectively used for
catalytic purposes. PSMs can either extend the MOF framework with catalytically
active functionalities or contribute to defect engineering for open metal site formation.
Moreover, combining different modifying procedures has been introduced as a tandem
approach when various reactions prompt several changes in the framework. Epitaxial
growth was also presented as PSM, which can govern catalytically beneficial features
mostly for thin films, unattainable to achieve by conventional methods. Recent MOFs’
PSM findings were reviewed to show new pathways and a continuously developing
field of reticular chemistry which come across with the expectations for novel and
more efficient catalysts.
Keywords: Coordination sites, Epitaxial growth, Ligand exchange, Ligand functionalization, Ligand installation, Ligand removal, Linkers, Metal exchange, Metal incorporation, Metal–organic frameworks, Metal nodes, MOF, MOF stability, Post-synthetic modification, PSM, Redox transformations, Transme-talation.
