Single-Atom Dopants in Plasmonic Nanocatalysts

Bimetallic nanostructures combining plasmonic and catalytic metals are promising for tailoring and enhancing plasmonic hot-carrier generation utilized in plasmonic catalysis. In this work, we study the plasmonic hot-carrier generation in noble metal nanoparticles (Ag, Au, and Cu) with single-atom dopants (Ag, Au, Cu, Pd, and Pt) with first-principles time-dependent density functional theory calculations. Our results show that the local hot-carrier generation at the dopant atom is greatly altered by the dopant element while the plasmonic response of the nanoparticle as a whole is not significantly affected. In particular, hot holes at the dopant atom originate from the discrete d-electron states of the dopant, and the energies of these d-electron states and hence those of the hot holes depend on the dopant element, which opens up the possibility to tune hot-carrier generation with suitable dopants.