Heterogenization of Molecular Electrocatalytic Active Sites through Reticular Chemistry

Abstract

The electrochemical conversion of small molecules, such as CO2, O2, and H2O, has received significant attention as a potential engine for sustainable life. Metal–organic frameworks (MOFs) are a promising class of electrocatalytic materials for such processes. An attractive aspect of utilizing this class of materials as electrocatalysts is that well‐known molecular active sites can be introduced to well‐defined crystalline heterogeneous catalytic systems with high tunability. This review offers strategic insights into recent studies on MOF‐based electrocatalysts by discussing the notable active sites that have been utilized in both homogeneous and heterogeneous catalysts, while highlighting instances where such active sites have been introduced into MOFs. In addition, material design principles enabling the integration of electrochemically active components with the MOF platform are outlined. Viewpoints on the viability of MOFs as an alternative to currently used electrocatalysts are also discussed. Finally, the future direction of MOF‐based electrocatalysis research is established.

Electrocatalysis with molecules and molecular assemblies within gas diffusion electrodes

“…25 These entail molecules adsorbed, grafted, or grown on heterogeneous electrodes, 13 as well as MOFs/COFs deposited/grown on electrode surfaces. 26–28 Heterogenized molecular systems have advantages since their active sites are ‘wired’ to the electrode the entire time while still being accessible to reactants in the electrolyte, a situation more closely resembling heterogeneous material electrocatalysts. One key additional parameter is the link between the catalyst and electrode, which plays a determining role in stability (minimizing desorption) and activity (facilitating electron transfer).…”

Metal–Organic-Framework-Based Nanoarrays for Oxygen Evolution Electrocatalysis

“…55 The tunability and spatial arrangement of MOF structures make it possible for them to introduce various active species to achieve high catalytic activity. 56 Recent studies have revealed that the surface of MOFs undergoes reconstruction in the OER process to form metal hydroxides/oxyhydroxides with abundant defects that are induced by the porous structure and the presence of ligands in MOFs. 57−59 This makes MOFs a promising class of pre-electrocatalysts for the OER.…”

“…The inorganic–organic combination of MOFs can generate infinite possibilities, giving them characteristics such as adjustable pores, ultrahigh specific surface area, controllable composition, and diverse coordination modes. − Especially, benefiting from the high density of metal active sites, the pristine MOFs with diverse MO 6 -based inorganic units have shown great potential in electrocatalysis . The tunability and spatial arrangement of MOF structures make it possible for them to introduce various active species to achieve high catalytic activity . Recent studies have revealed that the surface of MOFs undergoes reconstruction in the OER process to form metal hydroxides/oxyhydroxides with abundant defects that are induced by the porous structure and the presence of ligands in MOFs. − This makes MOFs a promising class of pre-electrocatalysts for the OER.…”

Preparation of one-dimensional coordination polymers of a flexible tripyridyl disulfide with diverse topologies

“…For the last three decades, traditional metal-ligand coordination chemistry has expanded the research area to coordination polymers with diverse topologies by employing linker ligand building blocks achieving huge progress both in scientific and technological applications by virtue of the new materials. [1][2][3][4][5][6][7][8] Of these, one-dimensional (1D) coordination polymers are the most fundamental in topologies. 2,9 Thus, the synthetic research for the 1D coordination polymers could be considered less interesting structurally even though diverse types of related nanomaterials including nanowires, nanotubes, nanorods, etc.…”