Advancing electrochemical N2 reduction: interfacial electrolyte effects and operando computational approaches

Abstract

The electrochemical N₂ reduction reaction (eNRR) is a promising pathway for clean and sustainable production of ammonia, a compound essential for global industry. The challenges of the eNRR lie in the complexity of the electrode–electrolyte interface (EEI). While advances have been made in tuning the electrolyte compositions, the understanding of underlying atomic-level mechanisms remains limited. Operando computational techniques are emerging as instrumental tools to address relevant issues. In this review, we highlight a path forward by summarizing the recent advances in engineering strategies for direct-eNRR, including cations, organic solvents, ionic liquids; and for indirect-NRR with the incorporation of lithium-mediators. Additionally, we summarized relevant computational techniques that can investigate the interfacial dynamic properties associated with electrolyte modifications within N₂ reduction. By promoting the application of these computational methodologies, this review contributes to the ongoing efforts towards the realization of highly efficient electrochemical N₂ reduction.