Exohedral M-C-60 And M-2-C-60 (M = Pt, Pd) Systems As Tunable-Gap Building Blocks For Nanoarchitecture And Nanocatalysis

Transition metal-fullerenes complexes with metal atoms bound on the external surface of C-60 are promising building blocks for next-generation fuel cells and catalysts. Yet, at variance with endohedral M@C-60, they have received a limited attention. By resorting to first principles simulations, we elucidate structural and electronic properties for the Pd-C-60, Pt-C-60, PtPd-C-60, Pd-2-C-60, and Pt-2-C-60 complexes. The most stable structures feature the metal atom located above a high electron density site, namely, the pi bond between two adjacent hexagons (pi-66 bond). When two metal atoms are added, the most stable configuration is those in which metal atoms still stand on p-66 bonds but tends to clusterize. The electronic structure, rationalized in terms of localized Wannier functions, provides a clear picture of the underlying interactions responsible for the stability or instability of the complexes, showing a strict relationship between structure and electronic gap. (C) 2015 AIP Publishing LLC.