C–Cl Bond Activation on Au/Pd Bimetallic Nanocatalysts Studied by Density Functional Theory and Genetic Algorithm Calculations

Abstract

The C–Cl bond activation by Au/Pd bimetallic alloy nanocatalysts has been investigated with regard to the oxidative addition of chlorobenzene (PhCl). Fifteen stable structures of the Au10Pd10 nanocluster (NC) obtained by a genetic algorithm were examined by DFT calculations using the M06-L, TPSS, and B3LYP functionals. Triplet states of cage-like C1 and Cs structures are found to be relevant reflecting the quasi-degenerate nature of the Pd moiety, while several other low-lying structures and spin states may also contribute to the oxidative addition. For all examined cluster structures, the oxidative addition step is exothermic, and internal conversion and/or spin crossing are expected to occur as several states are close in energy and geometry. Based on an energetic analysis of a model system consisting of the Au10Pd10 NC surrounded by four poly(n-vinylpyrrolidone) (PVP) molecules, the PVP units activate the system as electron donors and stabilize it. While a neutral NC model overestimates the energy barr...