Direct Visualization of a Gold Nanoparticle Electron Trapping Effect

Abstract

A new atomic-scale anisotropy in the photoreaction of surface carboxylates on rutile TiO₂(110) induced by gold clusters is found. STM and DFT+U are used to study this phenomenon by monitoring the photoreaction of a prototype hole-scavenger molecule, benzoic acid, over stoichiometric (s) s-TiO₂, Au₉/s-TiO₂, and reduced (r) Au₉/r-TiO₂. STM results show that benzoic acid adsorption displaces a large fraction of Au clusters from the terraces toward their edges. DFT calculations explain that Au₉ clusters on stoichiometric TiO₂ are distorted by benzoic acid adsorption. The influence of sub-monolayers of Au on the UV/visible photoreaction of benzoic acid was explored at room temperature, with adsorbate depletion taken as a measure of activity. The empty sites, observed upon photoexcitation, occurred in elongated chains (2 to 6 molecules long) in the [11̅0] and [001] directions. A roughly 3-fold higher depletion rate is observed in the [001] direction. This is linked to the anisotropic conduction of excited electrons along [001], with subsequent trapping by Au clusters leaving a higher concentration of holes and thus an increased decomposition rate. To our knowledge this is the first time that atomic-scale directionality of a chemical reaction is reported upon photoexcitation of the semiconductor.