Cation Substitution Strategy for Developing Perovskite Oxide with Rich Oxygen Vacancy-Mediated Charge Redistribution Enables Highly Efficient Nitrate Electroreduction to Ammonia

The electrocatalytic nitrate (NO3-) reduction reaction (eNITRR) is a promising method for ammonia synthesis. However, its efficacy is currently limited due to poor selectivity, largely caused by the inherent complexity of the multiple-electron processes involved. To address these issues, oxygen-vacancy-rich LaFe0.9M0.1O3-δ (M = Co, Ni, and Cu) perovskite submicrofibers have been designed from the starting material LaFeO3-δ (LF) by a B-site substitution strategy and used as the eNITRR electrocatalyst. Consequently, the LaFe0.9Cu0.1O3-δ (LF0.9Cu0.1) submicrofibers with a stronger Fe-O hybridization, more oxygen vacancies, and more positive surface potential exhibit a higher ammonia yield rate of 349 ± 15 μg h-1 mg-1cat. and a Faradaic efficiency of 48 ± 2% than LF submicrofibers. The COMSOL Multiphysics simulations demonstrate that the more positive surface of LF0.9Cu0.1 submicrofibers can induce NO3- enrichment and suppress the competing hydrogen evolution reaction. By combining a variety of in situ characterizations and density functional theory calculations, the eNITRR mechanism is revealed, where the first proton-electron coupling step (*NO3 + H+ + e- → *HNO3) is the rate-determining step with a reduced energy barrier of 1.83 eV. This work highlights the positive effect of cation substitution in promoting eNITRR properties of perovskites and provides new insights into the studies of perovskite-type electrocatalytic ammonia synthesis catalysts.