Advancing nitrate reduction to ammonia: insights into mechanism, activity control, and catalyst design over Pt nanoparticle-based ZrO₂

The reduction of nitrogen oxides (NOx) to NH3, or N-2 represents a crucial step in mitigating atmospheric NO3 and NO2 emissions, a significant contributor to air pollution. Among these reduction products, ammonia (NH3) holds particular significance due to its utility in nitrogen-based fertilizers and its versatile applications in various industrial processes. Platinum-based catalysts have exhibited promise in enhancing the rate and selectivity of these reduction reactions. In this study, we employ density functional theory (DFT) calculations to explore the catalytic potential of Pt nanoparticle (PtNP)-supported ZrO2 for the conversion of NO3 to NH3. The most favorable pathway for the NO3 reduction to NH3 follows a sequence, that is, NO3 -> NO2 -> NO -> ONH -> ONH2/HNOH -> NH2/NH -> NH2 -> NH3, culminating in the production of valuable ammonia. The introduction of low-state Fe and Co dopants into the ZrO(2 )support reduces energy barriers for the most challenging rate-determining hydrogenation step in NOx reduction to NH3, demonstrating significant improvements in catalytic activity. The incorporation of dopants into the ZrO2 support results in a depletion of electron density within the Pt cocatalyst resulting in enhanced hydrogen transfer efficiency during the hydrogenation process. This study aims to provide insights into the catalytic activity of platinum-based ZrO2 catalysts and will help design new high-performance catalysts for the reduction of atmospheric pollutants and for energy applications.