The promising 2D monolayers supported single f-electrons atom (Ce, Th, and U) catalysts in the ammonia synthesis via electrochemical nitrogen reduction reaction

The production of environmentally friendly through electrocatalytic nitrogen reduction under ambient conditions holds great promise for green energy. Efficient catalysts play a crucial role in this process. In this study, we employed density functional theory calculations to examine the catalytic performance of three types of monolayers, namely four surrounding N atom doped graphene sheet (GN4), graphdiyne, and Ti2CO2, supported by three different single atoms (Ce, Th, and U) with f-electrons. Our results identified that U@GN4 exhibits excellent catalytic activity through the distal pathway, with a ΔG of only 0.64 eV for the potential determining step. Furthermore, theoretical analysis reveals that the synergistic action of U d and f electrons plays a crucial role in the N2 reduction catalyzed by the U@GN4. The catalytic performance for hydrogen evolution was also examined for these nine single-atom catalysts. Th@GN4 and Th@Ti2CO2 demonstrate promising performance in hydrogen evolution, with ΔGH* of 0.03 and 0.10 eV, respectively. This study holds significant value for the design and utilization of single-atom catalysts with f-electrons for efficient N2 reduction reaction and hydrogen evolution reaction electrocatalysts.