Rate-potential decoupling: a biophysical perspective of electrocatalysis

In this perspective, the chemical physics of biological electron transfer are considered in relation to artificial electrocatalyst development. Nature’s ability to access a wide range of chemical reactivities through a narrow set of redox-active motifs, in part by decoupling electron transport rates from reaction driving forces, is suggested as a model for the future of electrocatalyst design and testing. Theoretical rationale and experimental precedents for this concept are put forth, outlining how emulating nature’s ability to arbitrarily tune tunneling currents with respect to donor/acceptor redox potentials may enhance our control of electrocatalyst selectivity.