Heterogeneous electrosynthesis of C–N, C–S and C–P products using CO₂ as a building block

Electrochemical CO₂ reduction (CO₂R) provides a sustainable route to produce carbon-based fuels. This Review explores the expansion of the scope and impact of CO₂R by coupling CO₂ with heteroatomic co-reactants. The societal demand for C–X (C–N, C–S and C–P) bond-containing chemicals is evaluated, and current synthetic routes for C–X bonds are examined. Established routes for heteroatom coupling are then contrasted with electrosynthetic approaches that use CO₂ as a building block, which are classified into three distinct categories: (1) surface–solution coupling, (2) co-reduction and (3) near-surface coupling. Within each category, key aspects of the catalyst, reactor and molecule-specific reactivity that enable the coupling pathway are examined. The Review is concluded with a forward-looking discussion of required developments in electrocatalytic chemistry and how computational tools may accelerate progress. Finally, we examine upcoming challenges in both system design and technoeconomics that need to be addressed as this technology matures.