Single Transition Metal Atom Bound to the Unconventional Phase of the MoS₂Monolayer for Catalytic Oxygen Reduction Reaction: A First-Principles Study

Supported single-atom catalysts (SACs) have received a lot of attention due to their super-high atom utilization and outstanding catalytic performance. However, the instability of the supported transition-metal (TM) atoms hampers their widespread applications. Exploration of an appropriate substrate to stabilize the supported single atom is crucial for the future implementation of SACs. In recent years, two-dimensional materials have been proposed as possible substrates due to their large specific surface areas, but their chemically inert surfaces are difficult to stabilize TM atoms without defecting or doping. Herein, by means of systematic first-principles calculations, we demonstrate that the defect-free MoS2 monolayer in the unconventional phase (1T′) can effectively immobilize single TM atoms owing to its unique electrophilic property as compared to the conventional 2H phase. As a prototype probe, we investigated oxygen reduction reaction (ORR) catalyzed by a total of 21 single TM atoms stabilized on 1T′-MoS2 and successfully screened out two candidates, Cu and Pd@1T′-MoS2, which have a low overpotential of 0.41 and 0.32 V respectively, outperforming most of the previously reported ORR catalysts. Furthermore, we reveal that the adsorption energy of the ORR intermediate, *OH, provides an excellent descriptor to assess the ORR activity, which is further determined by the d-band center of the supported TM adatoms, thus being a great advantage for future design of stable and high-performance SACs.