Direct Visualization of a Gold Nanoparticle Electron Trapping Effect

Oscar Bentley Jerdmyr Williams, Khabiboulakh Katsiev, Byeongjin Baek, George Harrison, G. Thornton, Hicham Idriss

Research output: Contribution to journalArticlepeer-review

3 Scopus citations

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.
Original languageEnglish (US)
JournalJournal of the American Chemical Society
DOIs
StatePublished - Jan 5 2022

ASJC Scopus subject areas

  • Biochemistry
  • Colloid and Surface Chemistry
  • Chemistry(all)
  • Catalysis

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