The Challenge of Electrochemical Ammonia Synthesis: A New Perspective on the Role of Nitrogen Scaling Relations

Abstract The electrochemical production of NH 3 under ambient conditions represents an attractive prospect for sustainable agriculture, but electrocatalysts that selectively reduce N 2 to NH 3 remain elusive. In this work, we present insights from DFT calculations that describe limitations on the low‐temperature electrocatalytic production of NH 3 from N 2 . In particular, we highlight the linear scaling relations of the adsorption energies of intermediates that can be used to model the overpotential requirements in this process. By using a two‐variable description of the theoretical overpotential, we identify fundamental limitations on N 2 reduction analogous to those present in processes such as oxygen evolution. Using these trends, we propose new strategies for catalyst design that may help guide the search for an electrocatalyst that can achieve selective N 2 reduction.