Electrocatalytic Reduction of Nitric Oxide to Ammonia on Defective ZnIn ₂ S ₄

The electrocatalytic nitric oxide reduction reaction (NORR) is a sustainable approach for converting the gas pollutant nitric oxide (NO) into value‐added ammonia (NH 3 ). Currently, electrocatalytic synthesis remains a significant challenge due to the limited understanding of theoretical principles for designing highly active and selective catalysts. Herein, for the first time, hexagonal ZnIn 2 S 4 with a sulfur vacancy (V S ) as a potential NORR catalyst is systematically investigated using first‐principles calculations. The hybridization between 5 p orbital of the indium (In) atom and absorbed NO leads to a strong interaction between the substrate and the adsorbate. The catalyst demonstrates excellent performance with a low limiting potential and prevents the formation of byproducts. Additionally, the hydrogen evolution reaction can be completely inhibited due to the deviation of the proton adsorption from the optimal zero value. Different from conventional d ‐block transitional metal catalysts, here, the exposed p ‐block indium acts catalytically active center for NORR. This work not only highlights a new sustainable catalyst for NORR but also offers an effective strategy for designing novel catalysts.