Multifunctional Carbon‐Based Metal‐Free Catalysts for Cascade Electrochemical‐Chemical Coupling Catalyses

Abstract Cascade electrochemical‐chemical coupling (CECC) involves sequential electrochemical and chemical reactions, using intermediates from electrochemical processes as reactants for subsequent chemical transformations to enhance the efficiency and selectivity for sustainable syntheses of complex chemicals. Despite its economic and environmental benefits, CECC still faces multiple challenges, including a low utilization of intermediate reactants, competitive side reactions, and difficulties in the design and scale‐up of catalysts, leading to low selectivity and yield. To ensure economically viable CECC, it is imperative to rationally design and develop cost‐efficient and high‐performance catalysts, such as carbon‐based metal‐free electrocatalysts (C‐MFECs) and certain carbon‐supported transition metal catalysts, with high activity and selectivity for atomic precision syntheses of desirable products. In this review, an overview of recent advancements in the doping of C‐MFECs is provided for enhancing their catalytic activity and selectivity toward CECC. Three major CECC catalytic systems based on C‐MFECs are discussed; they are hydrogen peroxide coupling, carbon dioxide upgrading, and redox‐mediated systems. Current challenges and future perspectives in this emerging field are also addressed.