Cyrille Costentin, Marc Robert, and Jean-Michel Savéant
Laboratoire d'Electrochimie Moléculaire, UMR 7591 CNRS, Université Paris Diderot, Sorbonne Paris Cité, 15 rue Jean-Antoine de Baïf, F-75205 Paris Cedex 13, France
Molecular catalysis of electrochemical reactions currently attracts a lot of attention, notably concerning the transformation of small molecules in response to issues raised by modern energy challenges. This review summarizes recent advances in the mechanism analysis of multi-electrons–multi-steps processes involved in homogenous molecular catalysis of such electrochemical reactions. It also describes strategies for a rational catalyst benchmarking, through the establishment of “catalytic Tafel plots”. We show that careful analysis of through-structure and through-space substituent effects within a given family of catalyst is a powerful tool for intelligent design of new catalysts. Challenges raised by the “heterogenization” of molecular catalysts are discussed in the final section.