Methane activation on single-atom Ir-doped metal nanoparticles from first principles.

The breaking of the C–H bond of CH4 is of great importance, and one of the most efficient strategies in heterogeneous catalysis is to alter the electronic structure of a surface by doping it with different metal elements or controlling the stoichiometry. We present an in-depth study on methane activation on pure metal and single-atom Ir-doped alloy nanoparticles, which are constructed based on (100), (110), (111) surfaces using density functional theory (DFT) calculations. DFT results show that the dissociation barriers of CH4 on the Ir-doped alloy surfaces are about 0.3–0.4 eV, much lower than those on the pure metal surfaces (i.e., 0.6–0.8 eV). DFT-based transition state theory further reveals the rates of the first C–H activation on single-atom Ir-doped alloy nanoparticles at the early stages. Importantly, a strong temperature dependence is mainly contributed by the proportion of the exposed (110) surface. The Ir-doped Pt nanoparticle is found to be an efficient catalyst for methane activation in potential industrial applications. These important results are helpful for further designing new metal catalysts for methane activation at the atomic/molecular level.