FeVO4 porous nanorods for electrochemical nitrogen reduction: contribution of the Fe2c–V2c dimer as a dual electron-donation center

Abstract

The electrocatalytic N₂ reduction reaction (NRR) offers a sustainable route for ambient NH₃ production. To ensure a high NRR efficiency, it is critically important to design active electrocatalysts which possess a strong electron-donating capability to activate the stable NN bond and facilitate the protonation process. Herein, inspired by the FeV-cofactor as a catalytic site for biological N₂ fixation, we show that the FeVO₄ can be a highly efficient and durable NRR catalyst. The developed FeVO₄ porous nanorods delivered a favorable combination of both high NH₃ production rate (52.8 μg h⁻¹ mg⁻¹) and high faradaic efficiency (15.7%), surpassing those of nearly all the previously reported Fe- and V-based catalysts. Theoretical computations revealed that the high NRR performance of FeVO₄ originated from the Fe_2c–V_2c dimer (2c means two-fold coordinated bond) as a dual electron-donation center to effectively activate the NRR with a low overpotential.