Electron Spin in Electrocatalytic Nitrogen Reduction Reactions from Mechanistic Understanding to Catalyst Design

Investigating the regulatory mechanism of electron spin in the electrocatalytic nitrogen reduction reaction (NRR) is of great significance for advancing the development of efficient electrocatalysts. As one of the most promising green technologies for ammonia production, electrochemical nitrogen fixation offers high Faradaic efficiency and favorable ammonia yield. However, its large-scale application is still hindered by the limited availability of catalysts with high activity, selectivity, and stability. As an intrinsic property of electrons, spin regulation during the reaction process can significantly enhance catalytic performance. This review first summarizes recent progress in electrocatalytic NRR, highlighting its advantages as a novel route for sustainable ammonia synthesis while addressing the current technical challenges. The generation conditions and influencing factors of electron spin are systematically discussed, followed by an overview of common spin regulation strategies, including internal structural tuning of materials and external physical field modulation. Representative studies are introduced to illustrate the application of spin effects in related scientific domains. By focusing on two key bottlenecks in the NRR processnamely, the activation of nitrogen molecules and the stabilization of reaction intermediatesthis review further explores the potential of electron spin regulation to enhance catalytic activity and stability. Finally, the future development trends and application prospects of spin effects in electrocatalytic NRR are discussed. This work aims to deepen the understanding of spin regulation mechanisms and provide theoretical guidance for the rational design of next-generation high-performance electrocatalysts.