Abstract
Heterometallic coordination polymers have been rapidly developed as heterogeneous electrocatalysts. This review highlights the synthesis strategies of these polymers and the relationships between structures and electrocatalytic performances.
Highlights
Coordination polymers (CPs) are crystalline solids with infinite structures that are sustained by coordination bonds between metal ions or metal clusters and organic linker molecules, including metal–organic frameworks (MOFs) as a CP sub-Naoto Kuwamura received hisB.S., M.S. and Ph.D. degrees from Osaka City University in2006, 2008 and 2011, respectively
While CPs have been applied to obtain inorganic composite materials by their pyrolysis in materials science, recently, an increasing number of studies have been conducted on their direct employment as heterogeneous electrocatalysts because they are (i) crystalline compounds whose molecular and Review packing structures can be determined at an atomic-level resolution by X-ray crystallography, (ii) solid materials that can offer high stability in the solid state, and (iii) hybrid compounds that contain metal ions available for catalytically active sites
Heterogeneous electrocatalytic reactions using heterometallic CPs containing more than two kinds of metal ions, which can be prepared by the self-assembly of metal ions and ligands in a one-pot reaction, the metalloligand approach using metal complexes with several donor sites, or the post-synthesis modification of CPs by metal exchange reactions, are a recent hot topic in this research area, because their metal centres cause synergistic and cooperative effects in electrocatalytic reactions
Summary
Coordination polymers (CPs) are crystalline solids with infinite structures that are sustained by coordination bonds between metal ions or metal clusters and organic linker molecules, including metal–organic frameworks (MOFs) as a CP sub-. The incorporation of several kinds of metal ions in a single CP structure has commonly been achieved by one-pot reactions in which different kinds of metal ions with different coordination properties are mixed with organic ligands.[25] Another method to achieve this, so-called metalloligand approach, is the use of isolated metal complexes that possess donor site(s) for binding metal ions to form heterometallic multinuclear structures.[26] Following the first section, the relevance of the structural aspects of CPs, such as their dimensionalities, combinations of metal ions, coordination environments, and porosities, to their electrocatalytic activities is described, together with representative examples. Other hand, the synthesis situation of heterometallic CPs is different, and three synthesis techniques have been applied to incorporate two or more kinds of metal ions into polymer structures (Fig. 1): (i) a self-assembly method (or one-pot synthesis), (ii) a metalloligand approach,[33] and (iii) post-synthesis modification.[34]. This method allows for the control of the structures and dimensionalities of CPs via the proper choice of metalloligands and target metal ions, which act as the nodes and linkers in the produced polymeric
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