Structure−Reactivity Correlations in Pd−Au Bimetallic Nanoclusters

Abstract

The effect of composition and morphology of bimetallic Pd-Au nanoclusters on their chemical reactivity has been studied with acetylene decomposition and conversion to ethylene and benzene as the chemical probe. High resolution transmission electron microscopy (HR-TEM) and CO-Temperature Programmed Desorption (TPD) measurements were employed for structure and chemical composition determination. Pd-Au clusters were prepared in ultrahigh vacuum (UHV) environment on SiO(2)/Si(100) by direct deposition (DD) to form 2D bimetallic nanostructures. Different bimetallic cluster morphology could be obtained by employing the buffer layer assisted growth (BLAG) procedure with amorphous solid water as buffer material. The BLAG bimetallic clusters were found to be more reactive than DD particles toward acetylene hydrogenation to ethylene and trimerization to benzene. The morphology and composition of DD clusters enabled the formation of both tilted (low adsorption energy) and flat laying (high adsorption energy) benzene, while mainly tilted benzene was detected upon adsorption of acetylene on BLAG clusters. Moreover, the reactivity of bimetallic clusters was compared to that of thin Pd film. Strong preference (100:1 ratio) toward acetylene hydrogenation to ethylene over trimerization to benzene has been correlated with the lack of extended Pd(111) facets on the bimetallic clusters that suppress the benzene formation.