Design of Fe₂Mo@γ-GDY triatomic catalyst for electrocatalytic urea synthesis of N₂ and CO: a theoretical study

While urea is widely used as a chemical raw material, its precursor ammonia (NH3) has traditionally been synthesized under high-temperature/pressure conditions, leading to not only huge energy consumption but also serious CO2 emission. Here, we present a groundbreaking catalyst design approach, which optimizes adsorption configurations and reaction pathways by controlling the adsorption energies of each intermediate in the reaction, thus enhancing catalytic performance. Via density functional theory (DFT) calculations, we designed a triatomic catalyst [i.e., Fe2Mo@γ-graphdiyne (γ-GDY)] with a limiting potential of -0.22 V and a C-N coupling energy barrier of 0.34 eV. Notably, the Fe2Mo@γ-GDY catalyst presents a high selectivity and robust antioxidation capabilities under applied potentials. Our comprehensive analysis elucidates the factors affecting the limiting potential and C-N coupling energy barrier. These insights significantly contribute to the advancement of catalyst design strategies for electrocatalytic urea synthesis, offering a more efficient and eco-friendly alternative to traditional methods.