Surface structural characteristics and tunable electronic properties of wet-chemically prepared Pd nanoparticles

The ligand substitution reaction, Pd L-3,L-2,L-1-edge and S K-edge x-ray absorption fine structure (XAFS), XAFS simulations, and valence-band and core-level x-ray photoelectron spectroscopy (XPS) have been used to systematically study the surface chemical and electronic properties of wet-chemically prepared Pd nanoparticles of varied size, molecular capping, and metal composition. It was found that the replacement of weakly interacting capping molecules (amine and tetra-alkylphosphonium bromide) with strongly binding thiols caused a considerable change in the surface bonding of Pd nanoparticles. However, the Pd d-electron counts (number of d electrons) remained almost unchanged before and after ligand substitution, which is unexpected since Pd atoms normally lose electrons to the more electronegative S atoms. XAFS results and simulations provided useful insights into the surface structural characteristics of Pd nanoparticles and satisfactorily accounted for the unexpected d-electron behavior involved in the ligand substitution process. XPS valence and core-level spectra further revealed a size-dependent d-band narrowing and presented complementary information to XAFS about the surface electronic properties of Pd atoms. The small weakly bound Pd nanoparticles seem inevitably to have a net d-electron depletion due to the influence of the surface effect (chemical adsorption by oxygen), which is more significant than the d-electron enriching nanosize effect. However, it was demonstrated that by forming Pd-Ag alloy nanoparticles, a net increase of the Pd d-electron counts can be realized. Therefore, it is illustrated that by manipulating the surface, size, and alloying effects, the electronic properties of Pd nanoparticles can be possibly tuned. (c) 2008 American Institute of Physics.