Predictive Theoretical Model for the Selective Electroreduction of Nitrate to Ammonia

The electrochemical reduction of nitrate (eNO₃RR) emerges as a promising route for decentralized ammonia synthesis. However, the competitive production of nitrite at low overpotentials is a challenging issue. Herein, using the combination of density functional theory and microkinetic modeling, we show that the selectivity for NH₃ surpasses that of NO₂⁻ at -0.66 VRHE, which nicely reproduced the experimental value on titania. NH₂OH* → NH₂* is the kinetically controlling step at a low overpotential for NH₃ generation, while NO₂* → HNO₂ has the highest barrier to producing nitrite. Based on these mechanistic insights, we suggest that ΔG₁ (NH₂OH* → NH₂*) - ΔG₂ (NO₂* → HNO₂) can serve as a descriptor to predict the S(NO₂⁻)/S(NH₃) crossover potential. Such a model is verified by the experimental results on Ag, Cu, TiO2-x, Fe₃O₄, and Fe-MoS₂ and can be extended to the Au catalyst. Thus, this work sheds light on the rational design of catalysts that are simultaneously energy-efficient and selective to NH₃.