Electrochemical Conversion of Inert Small Molecules for Sustainable Chemistry

Comprehensive Summary The sustainable electrochemical conversion of inert small molecules, such as N 2 , CH 4 , and CO 2 , is opening new frontiers in green chemistry and energy technologies. Each of these molecules can be individually converted into a valuable chemical, offering the potential to replace existing industrial processes. Electrochemical N 2 reduction to NH 3 could replace the Haber‐Bosch process, avoiding the high‐temperature and high‐pressure conditions. Beyond NH 3 , N 2 fixation is expanding toward diverse nitrogen‐containing chemicals. The catalytic oxidation of CH 4 is referred to as the “Holy Grail” reaction, as it is difficult to activate the first C–H bond and control the product selectivity. Nevertheless, CH 4 oxidation under mild electro/photo‐electrochemical conditions enables the facile activation of the inert C–H bond, and the selectivity can be efficiently adjusted by exquisitely designing the electrode interface. Electrocatalytic CO 2 reduction is a key technology for achieving carbon neutrality. Currently, the reaction continues to advance from mono‐carbon toward multi‐carbon products with improved activity and stability. In addition to the individual conversion of these inert small molecules, intermolecular coupling reactions such as C–N coupling reaction between N 2 and CO 2 provide further opportunities for electrochemical reactions. Collectively, these efforts represent a paradigm shift from fossil‐based processes toward scalable, eco‐friendly pathways for value‐added chemicals.