Construction of C-N bonds from small-molecule precursors through heterogeneous electrocatalysis.

Energy-intensive thermochemical processes within chemical manufacturing are a major contributor to global CO emissions. With the increasing push for sustainability, the scientific community is striving to develop renewable energy-powered electrochemical technologies in lieu of CO-emitting fossil-fuel-driven methods. However, to fully electrify chemical manufacturing, it is imperative to expand the scope of electrosynthetic technologies, particularly through the innovation of reactions involving nitrogen-based reactants. This Review focuses on a rapidly emerging area, namely the formation of C-N bonds through heterogeneous electrocatalysis. The C-N bond motif is found in many fertilizers (such as urea) as well as commodity and fine chemicals (with functional groups such as amines and amides). The ability to generate C-N bonds from reactants such as CO, NO or N would provide sustainable alternatives to the thermochemical routes used at present. We start by examining thermochemical, enzymatic and molecular catalytic systems for C-N bond formation, identifying how concepts from these can be translated to heterogeneous electrocatalysis. Next, we discuss successful heterogeneous electrocatalytic systems and highlight promising research directions. Finally, we discuss the remaining questions and knowledge gaps and thus set the trajectory for future advances in heterogeneous electrocatalytic formation of C-N bonds.