Reductive Inner-Sphere Electrosynthesis of Ammonia via a Nonelectrocatalytic Outer-Sphere Redox

Electrochemistry of outer-sphere redox molecules involves an essentially intact primary coordination sphere with minimal secondary sphere adjustments, resulting in very fast electron transfer events even without a noble metal-based electrocatalyst. Departing from conventional electrocatalytic paradigms, we incorporate these minimal reaction coordinate adjustments of outer-sphere species to stimulate the electrocatalysis of energetically challenging inner-sphere substrates. Through this approach, we are able to show an intricate 8e^- and 9H⁺ transfer inner-sphere reductive electrocatalysis at almost half the energy input of a conventional inner-sphere electron donor. This methodology of employing outer-sphere redox species has the potential to notably improve the cost and energy benefits in electrochemical transformations involving fundamental substrates such as water, CO₂, N₂, and many more.