LAUSR

Recent experiments about the selective coating of transition-metal oxide on Pt nanoparticles have aroused great interest in molecular catalysis for the promotion of both activity and stability. In this work, first-principles calculations combined with microkinetic methods are employed to shed light on the edge-selective growth mechanism of 3d-transition metal oxide on Pt nanoparticles in atomic layer deposition (ALD) from the metal cyclopentadienyl precursors (MCp2, M = Fe, Co, and Ni). The MCp2 decomposition on the surface of Pt nanoparticles exhibits robust preferential growth, following the order of edge > (100) > (111), which indicates that edges are naturally selected to be covered and the (111) facets could survive toward the MCp2 precursors. The preferred deposition on the edge site is attributed to a more favorable splitting path for the precursors. On the other hand, competing reactions make the overall reaction rates of MCp2 precursors on edge sites follow the order of NiCp2 > FeCp2 > CoCp2. Mor...