Title:Creation of Porous Coordination Polymers with Desired Functionality for Adsorptive Separation, Catalysis and Electrocatalysis
VOLUME: 7 ISSUE: 2
Author(s):S.V. Kolotilov*, A.S. Lytvynenko and S.A. Sotnik
Affiliation:L.V. Pisarzhevskii Institute of Physical Chemistry of the National Academy of Sciences of Ukraine, Prospect Nauki 31, 03028 Kiev, L.V. Pisarzhevskii Institute of Physical Chemistry of the National Academy of Sciences of Ukraine, Prospect Nauki 31, 03028 Kiev, L.V. Pisarzhevskii Institute of Physical Chemistry of the National Academy of Sciences of Ukraine, Prospect Nauki 31, 03028 Kiev
Keywords:Porous coordination polymers, metal-organic frameworks, selective sorption, catalysis, electrocatalysis, design,
post-synthetic modification.
Abstract:Background: Porous coordination polymers (PCPs) are widely used as sorbents and catalysts
for various processes. However, in the majority of cases the researchers can not predict the structure
(and, as a consequence, the properties) of a new coordination polymer. The coordination polymer for
special application is usually selected from the library of reported and characterized compounds, and
then its properties are tested. This review deals with design of PCPs for the specific sorption, separation
or catalytic applications.
Objectives: The objective of the review was to analyze and summarize the cases when porous coordination
polymers were specially designed for adsorption of certain substrates or catalysis of certain reaction.
Methods: The review summarized the results, obtained by X-ray structure determination, measurements
of different compounds adsorption from gaseous or liquid phase, and studies of catalytic and electrocatalytic
properties. Catalysis of organic reaction in solutions at presence of solid PCPs is considered.
Electrocatalytic activity was evaluated by cyclic voltammetry or by preparative electrolysis with solid
electrodes, modified by film of PCP.
Results: The approaches for creation of PCPs with desired sorption and catalytic properties were based
on selection of the specific fragments, functional groups or units with desired properties before synthesis
of the PCP, followed by creation of the PCP containing such specially designed units, or adjustment
of the PCP's structure in order to satisfy certain requirement. Sorption selectivity could be adjusted by
tuning of pore size in the PCP by variation of the ligand in isoreticular row of the compounds; introduction
of the functional groups, which have different binding energy in respect to various substrates or
tuning of the PCP's framework flexibility by appropriate choice of the ligands. Desired catalytic activity
could be achieved by use of the fragments, groups or units, which showed desired properties in the separate
experiments before their incorporation in the PCP.
Conclusion: There are several methods for achievement of the target selectivity or catalytic activity,
such as pre-synthetic choice or post-synthetic incorporation of functional groups, favorable for desired
substrate binding, or active sites for desired catalytic or electrocatalytic reactions. Despite seeming difference
of separation and catalytic applications, these methods are quite similar.