Design of MoS₂ edge-anchored single-atom catalysts for propane dehydrogenation driven by DFT and microkinetic modeling

The design of efficient catalysts for direct propane dehydrogenation (PDH) to inhibit coke formation and deactivation of traditional Pt-based catalysts are challenging tasks. Herein, by exploiting the unique geometric feature and tunability of single atom catalysts (SACs), a wide range of 3d-5d transition metals anchored on the MoS2 edge in the single atom form (TM1-S-4/edge) are comprehensively investigated for the PDH application by first-principles calculations, ab initio molecular dynamics (AIMD) simulations and microkinetic modeling. Five criteria are assessed in terms of the feasibility of preparation, practical stability, feasibility of recovery after air oxidation, activity and selectivity. We identified Ru-1-S-4/edge SAC as the most promising candidate with activity six times higher than that of the conventional Pt(111) catalyst. Interestingly, AIMD simulations show that the motif region of the highly reactive TM1-S-4/edge SACs (such as Ru, Os, Rh, and Ir) exhibits a dynamic change, with a TM-coordinated S atom tending to flutter at reaction temperatures and return to its initial position when the species is adsorbed on TMs, thereby affecting the PDH activities. In addition to identifying the potential PDH catalyst from a practical application point of view, we believe that this study also provides a comprehensive picture for the theoretical screening of low-coordination single-atom catalysts.