Overall Electrochemical N ₂ Fixation to Ammonia and Nitrate by Iridium‐Incorporated WO ₃ Nanorods and Sustainable Zn─N ₂ Battery Application

Abstract In this work, an iridium‐incorporated tungsten trioxide nanorod (Ir‐WO ₃ ) electrocatalyst is reported exhibiting bifunctional activity toward fixing N ₂ into ammonia and nitrate and showing higher activity than the pristine WO ₃ . The 5% Ir‐WO ₃ achieves a maximum ammonia yield rate of 17.60 µg h ⁻¹ mg _cat ⁻¹ with a faradaic efficiency of 19.42% at −0.4 V. Also, the 5% Ir‐WO ₃ achieves a maximum nitrate yield rate of 20.31 µg h ⁻¹ mg _cat ⁻¹ at 2.1 V with a faradaic efficiency of 27.34% at 1.9 V. Furthermore, the electrocatalyst possesses cyclic stability up to five consecutive cycles and long‐term durability of more than two days for both nitrogen reduction reaction (NRR) and nitrogen oxidation reaction (NOR). The density functional theory (DFT) analysis reveals that the initial protonation and oxidation of the dinitrogen molecule are the potential‐determining steps (PDS) for NRR and NOR, respectively. The introduction of Ir atoms boosts the adsorption and activation of N ₂ , diminishes the energy barrier, and improves the yield of ammonia and nitrate. To validate the real‐field application, the as‐prepared 5% Ir‐WO ₃ ‐based rechargeable aqueous Zn─N ₂ battery is assembled, which delivers a maximum power density of 3.79 mW cm ⁻² , a maximum ammonia yield rate of 6.39 µg h ⁻¹ mg _cat ⁻¹ , and a maximum energy density of 143 mWh g _zn ⁻¹ .