Enabling Unconventional “Alternating‐Distal” N2 Reduction Pathway for Efficient Ammonia Electrosynthesis

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.