Theoretical investigation of Fe-corrolazine-based single-atom electrocatalysis for NO-to-NH3 conversion

The electrochemical conversion of NO into value-added NH₃ presents a promising strategy for addressing energy challenges and mitigating environmental pollution. Although noble metal-based catalysts currently predominate in electrocatalytic NO reduction reaction (eNORR) research, their practical deployment remains constrained by excessive costs and limited atomic utilization efficiency. Non-noble metal corrolazines have shown remarkable catalytic capabilities in homogeneous systems, presenting innovative possibilities for eNORR implementation. Herein, we engineered a two-dimensional Fe-corrolazine single-atom catalyst (2D-Fe_cor SAC) through alkynyl-bridged assembly of Fe-corrolazine units. Then extensive density functional theory (DFT) calculations were conducted to explore its structural and electronic properties, as well as its eNORR catalytic behavior. The results show 2D-Fe_cor SAC exhibits excellent stability, and each Fe atom retains its catalytic active center, which can effectively adsorb and activate NO. Notably, 2D-Fe_cor SAC exhibits superior eNORR performance via an N-distal pathway, achieving a low limiting potential of −0.44 V with significant suppression of the hydrogen evolution reaction (HER). Crucially, aqueous environments enhance the catalytic efficiency and further reduce the limiting potential to −0.18 V. This significant activity originates from synergistic effects: the corrolazine framework enables precise electron transfer modulation while Fe centers facilitate efficient charge transport. Our work establishes a novel approach for developing cost-effective electrocatalysts to simultaneously remediate NO pollution and produce sustainable ammonia.