Abstract: AuPd nanoalloys with tunable Pd concentrations have been synthesized and used as model catalysts. They have been directly imaged by high-angle annular dark-field scanning transmission electron microscopy and investigated by thorough analyses of their extended X-ray absorption fine structure, X-ray absorption near-edge structure, X-ray diffraction and X-ray photoelectron spectroscopy measurements. The bimetallic nanoparticles are embedded in a carbonaceous matrix and have almost an identical structure at the atomic level and the same electronic properties as AuPd bulk alloys with the same compositions. The d-electron increase at surface Pd sites is determined by the Pd concentration of the alloy. Similarly, their activation entropy and catalytic activity for the hydrogenation of quinoline is related to the Pd concentration, with Au₅₀Pd₅₀ the most active of the alloys investigated. An almost 11 times higher activity was achieved compared to a pure Pd catalyst. The experimentally measurable surface d charge at the Pd sites in the AuPd was found to linearly correlate with the activation entropy and catalytic activity for the hydrogenation of quinoline. The alloy structure is stable, showing negligible metal segregation, dissolution-redeposition and aggregation during the hydrogenation process which involves strong adsorption.

Key words: Surface d charge, AuPd alloy, Activation entropy, Quinoline, Hydrogenation