Highly‐selective Electrocatalytic Reduction of NO to NH3 using Cu Embedded WS2 Monolayer as Single‐atom Catalyst: A DFT Study

Electrocatalytic nitric oxide reduction reaction (NORR) is a promising method for generating NH3. However, developing a NORR catalyst for NH3 synthesis with low cost and high efficiency is still challenging. We here report a series of single‐atom catalysts (SACs), designed by embedding nine different transition metals from Sc to Cu in S‐vacant WS2 monolayer (TM@WS2), and investigate the electrocatalytic performance for NORR process using the dispersion‐corrected density functional theory (DFT) calculations. Among them, Cu‐based SAC shows a strong binding to the WS2 surface and high selectivity towards NORR process, and also it greatly inhibits the competing hydrogen evolution reaction (HER). Through ab initio molecular dynamics (AIMD) simulations, the thermal stability of SAC is assessed and found no structure deformation even at 500 K temperature. All possible reactive pathways including distal and alternating mode at both N‐ and O‐end configurations for NH3 production were explored. We predicted that the Cu@WS2 SAC exhibits remarkable catalytic activity and selectivity with lowest limiting potential of ‐0.41 V via the N‐alternating pathway. Our study emphasize that the transition metal dichalcogenide (TMDC) based SACs are potential candidates for converting NO to NH3, and this opens a new avenue in designing NORR catalysts with high catalytic performance.