“…The electronic property of d electron in pure and alloy Ag NPs was first theoretically investigated by density function theory (DFT) calculation. Thermodynamically, the doped metals (Au, Pt, and Pd) exhibit monomer model on M−Ag alloy NPs, meanwhile, Ag is more likely to be found at the surface because of its lower surface energy, and especially in position of low coordination number, 22 and consequently, the surface model for M (Au, Pt, and Pd)−Ag was built by orderly replacing the Ag atoms in the topmost surface layer with M (Au, Pt, and Pd) atoms and reoptimizing the geometries of the relative position of Ag and M atoms (Figure S4). Impressively, the d band centers of these Ag NPs relative to Fermi level (E f ) were calculated to be −4.12, −4.11, −3.95, and −3.94 eV for Ag, Au−Ag, Pt−Ag, and Pd−Ag NPs, respectively (Figures 3a and S4), clearly illustrating the upward shift behavior of d band centers to the Fermi level in alloy Ag NPs compared with pure Ag NPs.…”