Enhanced Activity and Selectivity for Nitrogen Reduction Reaction in Electrides‐Based Heterostructures: A DFT Computational Study

Abstract

AbstractDeveloping sustainable and efficient catalysts for ammonia synthesis from atmospheric molecular N2 under ambient conditions presents a significant 21st‐century challenge. Two‐dimensional heterostructures, particularly single‐atom catalysts (SACs) supported on two‐dimensional materials, have emerged as a promising avenue due to their remarkable catalytic activity and selectivity. Electrides, characterized by an abundance of free electrons and high surface activity, have attracted substantial attention in this context. Through density functional theory (DFT) calculations, this study proposes electride‐graphene heterostructures (EGHS) as catalysts to effectively regulate charge distribution at the catalytic center, facilitating the optimization of catalytic performance. The EGHS model addresses challenges related to excessive adsorbate binding, mitigating electron transfer compared to electride monolayer adsorption. This novel approach utilizes heterogeneous heterostructures to finely tune the catalytic site, optimizing electron input for enhanced catalysis. Based on the optimized charge transfer for N2 activation, the Cr‐doped EGHS (Cr@EGHS) exhibits a promising performance in the nitrogen reduction reaction, leading to, a relatively low limiting potential of −0.85 V and high selectivity. The hypothesis charge transfer depend on N2 activation is further supported by modulating the distance between component layers of heterostructure. These findings contribute to design principles for 2D heterostructure catalysts and offer a reference for experimental synthesis.