Direct Visualization of a Gold Nanoparticle Electron Trapping Effect
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ArticleAuthors
Williams, Oscar Bentley JerdmyrKatsiev, Khabiboulakh
Baek, Byeongjin

Harrison, George
Thornton, G.

Idriss, Hicham

KAUST Department
KAUST Solar Center (KSC)Physical Science and Engineering (PSE) Division
Surface Science and Advanced Characterisation, SABIC-CRD at King Abdullah University for Science and Technology (KAUST), Thuwal, 23955, Saudi Arabia
Date
2022-01-05Embargo End Date
2023-01-05Submitted Date
2021-11-18Permanent link to this record
http://hdl.handle.net/10754/675023
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A new atomic-scale anisotropy in the photoreaction of surface carboxylates on rutile TiO<sub>2</sub>(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-TiO<sub>2</sub>, Au<sub>9</sub>/s-TiO<sub>2</sub>, and reduced (r) Au<sub>9</sub>/r-TiO<sub>2</sub>. STM results show that benzoic acid adsorption displaces a large fraction of Au clusters from the terraces toward their edges. DFT calculations explain that Au<sub>9</sub> clusters on stoichiometric TiO<sub>2</sub> 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.Citation
Williams, O. B. J., Katsiev, K., Baek, B., Harrison, G., Thornton, G., & Idriss, H. (2022). Direct Visualization of a Gold Nanoparticle Electron Trapping Effect. Journal of the American Chemical Society. doi:10.1021/jacs.1c12197Sponsors
This work was supported by the European Research Council Advanced Grant ENERGYSURF and EPSRC (U.K.) (EP/L015277/1).Publisher
American Chemical Society (ACS)PubMed ID
34985273Additional Links
https://pubs.acs.org/doi/10.1021/jacs.1c12197https://discovery.ucl.ac.uk/10141905/1/Thornton_Williams%20et%20al%20revised.pdf
ae974a485f413a2113503eed53cd6c53
10.1021/jacs.1c12197
Scopus Count
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