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The electrochemical nitrogen reduction reaction (NRR) provides a sustainable alternative to green ammonia synthesis. However, challenges persist due to limited accessibility of N 2 molecules at the electrode interface and competition from abundant protons at catalytic active sites, resulting in low N 2 coverage and compromised selectivity. In this work, we investigate the critical role of potassium cations (K + ) in modulating the interfacial environment, particularly focusing on how varying K + concentrations influence N 2 adsorption, *NH 3 desorption, and hydrogen transfer (HT) mechanisms under operating electrochemical conditions. Our results demonstrate that a highly concentrated K + electrode interface significantly enhances N 2 adsorption and *NH 3 desorption, collectively leading to improved NRR selectivity, in alignment with the experimental observations. We further uncover insights into HT kinetics, identifying two key steps: protonation (HT 1 ) and diffusion (HT 2 ). Among these, diffusion (HT 2 ) is the rate-limiting step, driven by hydrogen bond connectivity and proton shuttling strength within the cation-induced microenvironments. Specifically, at a low applied potential, a highly concentrated K + interface exhibits weak connectivity and sluggish proton shuttling, therefore limiting NRR efficiency. However, microkinetic modeling (MKM) analysis indicates that optimizing electrode potential and electrolyte compositions can overcome these limitations by promoting proton shuttling. Last but not least, we also provide a detailed map of the interplay among K + molarity, electrode potential, and NH 3 selectivity. Our work offers critical insights to guide the improvement of NRR efficiency through electrolyte and microenvironmental modulation.
Jiang et al. (Mon,) studied this question.