Abstract
Molecular catalysts and their assemblies are important model systems in electrocatalysis. This is largely because their active sites, secondary coordination spheres, and reaction environments can be rationally modulated. Such experiments yield important insights into the structure-activity relationships that can be used to design improved catalysts or translated to more technologically mature systems. However, in the context of electrocatalysis, molecular catalysts are often dissolved in an electrolyte or heterogenized on an electrode that is completely submersed in an electrolyte (e.g. H-cell) or reaction setups that are not used in practical systems and use poorly soluble gaseous reactants like CO(2), CO, or O(2). This is beginning to change, with a growing emphasis being placed on investigating molecular catalysts and catalytic assemblies (e.g. metal/covalent organic frameworks and polymers with molecular active sites) in gas-diffusion electrodes (GDEs) that feed the reactant directly from the gas phase to the catalytic sites and enable industrially viable current densities. Against this backdrop, this perspective first details the emerging set of molecular catalyst-embedded GDE-based systems and what the community has learned thus far from these efforts. We next identify the gaps in knowledge and performance that are yet to be closed and offer strategies for exploring in this direction. Finally, we conclude with a forward-looking discussion that highlights several new avenues to be pursued with molecule-based GDE platforms and how this can accelerate progress in the electrocatalysis field as a whole.