Identifying electrocatalytic activity and mechanism of Ce_1/3NbO₃ perovskite for nitrogen reduction to ammonia at ambient conditions

Herein, a novel Ce_1/3NbO₃ perovskite is proposed as an efficient electrocatalyst to catalyze the nitrogen reduction reaction (NRR) at ambient conditions. Density functional theory calculations are firstly used to predict the potential N₂ activation ability of Ce_1/3NbO₃, and then, the Ce_1/3NbO₃ with a flower-like porous structure is prepared by a hydrothermal process and post calcination. Electrochemical tests reveal that such catalyst achieves a high NRR performance with the Faradaic efficiency of 6.87% and NH₃ yield of 10.34 µg h⁻¹ cm⁻² at −0.8 V vs RHE in 0.1 M Na₂SO₄, keeping up with many electrocatalysts reported recently. The mechanistic studies disclose that Nb atom is favorable as the efficient active site for NRR by the distal pathway, and Ce atom synergistically enhances the charge transfer during the NRR process. Our work provides an important reference to the rational design of the promising electrocatalysts for NRR.