关键字：TOTAL-ENERGY CALCULATIONS; AMMONIA-SYNTHESIS; CRYSTAL; EVOLUTION; TOOL

摘要：The electrochemical nitrogen reduction reaction (eNRR) is a promising pathway for nitrogen fixation. However, the practical application of eNRR is hindered by the low catalytic activity and selectivity of catalysts available. This theoretical investigation focuses on the activation of N-2 on the surface of Fe-P binary compounds and doped structures, demonstrating the effectiveness of quantifying the activation degree using charge transfer to N-2, bond length, and bond order of N-2 obtained by COBI analysis in searching for effective NRR catalysts. Electronic properties analysis reveals that the activation of N-2 is controlled by the d-band centers of transition metals, and Fe2P exhibits the highest d-band center, rendering it the most effective at activating N-2. Additionally, the activation of N-2 is significantly influenced by the 3d electron number of the transition element dopants, which results from the magnetic moment of catalytic sites and the variation in the d-p* interaction. Based on the activation relationship, doping with Mn-Se, Mn-S, Ti, and V is predicted to result in significantly higher catalytic activity with high NRR selectivity. Insights into the relationship obtained in this study between N-2 activation and the electronic structure can assist in understanding, designing, and modifying NRR catalysts on a fundamental level.

卷号：127

期号：36

是否译文：否