Redox Mediators in Homogeneous Co-electrocatalysis

Homogeneous electrocatalysis has been well studied over the past several decades for the conversion of small molecules to useful products for green energy applications or as chemical feedstocks. However, in order for these catalyst systems to be used in industrial applications, their activity and stability must be improved. In naturally occurring enzymes, redox equivalents (electrons, often in a concerted manner with protons) are delivered to enzyme active sites by small molecules known as redox mediators (RMs). Inspired by this, co-electrocatalytic systems with homogeneous catalysts and RMs have been developed for the conversion of alcohols, nitrogen, unsaturated organic substrates, oxygen, and carbon dioxide. In these systems, the RMs have been shown to both increase the activity of the catalyst and shift selectivity to more desired products by altering catalytic cycles and/or avoiding high-energy intermediates. However, the area is currently underdeveloped and requires additional fundamental advancements in order to become a more general strategy. Here, we summarize the recent examples of homogeneous coelectrocatalysis and discuss possible future directions for the field.

Automated summary

Homogeneous electrocatalysis has been extensively studied for the conversion of small molecules to useful products for green energy applications or as chemical feedstocks. However, their industrial application is hindered by the need for improved activity and stability. Inspired by naturally occurring enzymes, co-electrocatalytic systems with homogeneous catalysts and redox mediators (RMs) have been developed to enhance catalytic performance. RMs have been shown to increase catalyst activity and control selectivity, but additional advancements are needed for this approach to become more widely applicable.