Enabling Unconventional “Alternating‐Distal” N 2 Reduction Pathway for Efficient Ammonia Electrosynthesis

作者：Chu Zhang, Qing Wang, Zeyu Li, Hengjie Liu, Lixiang Zhong, Jiawei Liu, Zheng Wang, Runjie Wu, Pin Song, Wenjie Chen, Zeming Qi, Chunshuang Yan, Li Song, Qingyu Yan, Chade Lv · 发表于：Angewandte Chemie International Edition · 年份：2025 · DOI：10.1002/anie.202502957 · 被引用次数：40 · 研究领域：Ammonia Synthesis and Nitrogen Reduction、Caching and Content Delivery、Advanced Photocatalysis Techniques

Abstract The general understanding on the reaction path is that the electrocatalytic N 2 reduction follows either individual associative alternating or distal pathways, where efficient N 2 activation and selective NH 3 production are very challenging. Herein, an unconventional “alternating‐distal” pathway was achieved by shifting the “*NHNH 2 →*NH 2 NH 2 ” to “*NHNH 2 →*NH + NH 3 ” step to boost NH 3 synthesis with an amorphous CeMnO x electrocatalyst. In this unconventional process, N 2 activation was realized through π back donation on the Mn site, while the Mn/Ce dual active sites could regulate the intermediate configurations to avoid the nitrogen‐containing by‐product formation. Such “alternating‐distal” pathway was affirmed by in situ spectroscopic analyses and theoretical calculations. In a neutral media, an average ammonia production rate of 82.8 µg h −1 mg −1 and an outstanding Faradaic efficiency of 37.3% were attained. This work validated an unconventional mechanism in electrocatalytic ammonia synthesis, which might be extended to other catalytic process with multiple possible reaction paths.