Enhancing electrocatalytic <scp>N<sub>2</sub></scp> reduction via tailoring the electric double layers
Haolan Tao, Cheng Lian, Hao Jiang, Chunzhong Li, Honglai Liu, René van Roij
Abstract
Abstract The electrocatalytic nitrogen reduction reaction (NRR) for NH 3 synthesis is still far from being practical and competitive with the common Haber–Bosch process. The rational design of highly selective NRR electrocatalyst is therefore urgently needed, which requires a deep understanding of both the electrode–electrolyte interface and the mass transport of reactants. Here, we develop a theoretical framework that includes electric double layer (EDL), mass transport, and the NRR kinetics. This allows us to evaluate the roles of near‐electrode environment and N 2 diffusion on the NRR selectivity and activity. The EDL, as the immediate reaction environment, remarkably impedes the diffusion of N 2 to the cathode surface at high electrode potentials, which explains experimental observations. This article also gives microscopic insights into the interplay between N 2 diffusion and reaction activity under the nano‐confinement, providing theoretical guidance for future design of advanced NRR electrocatalytic systems.