Watching visible light-driven CO2 reduction on a plasmonic nanoparticle catalyst

Gayatri Kumari, Xueqiang Zhang, Dinumol Devasia, Jaeyoung Heo, Prashant K. Jain

Research output: Contribution to journalArticle

Abstract

Photocatalytic reduction of carbon dioxide (CO2) by visible light has the potential to mimic plant photosynthesis and facilitate the renewable production of storable fuels. Accomplishing desirable efficiency and selectivity in artificial photosynthesis requires an understanding of light-driven pathways on photocatalyst surfaces. Here, we probe with single-nanoparticle spatial resolution the dynamics of a plasmonic silver (Ag) photocatalyst under conditions of visible light-driven CO2 reduction. In situ surface-enhanced Raman spectroscopy captures discrete adsorbates and products formed dynamically on single photocatalytic nanoparticles, most prominent among which is a surface-adsorbed hydrocarboxyl (HOCO∗) intermediate critical to further reduction of CO2 to carbon monoxide (CO) and formic acid (HCOOH). Density functional theory simulations of the captured adsorbates reveal the mechanism by which plasmonic excitation activates physisorbed CO2 leading to the formation of HOCO∗, indicating close interplay between photoexcited states and adsorbate/metal interactions.

Original languageEnglish (US)
Pages (from-to)8330-8340
Number of pages11
JournalACS Nano
Volume12
Issue number8
DOIs
StatePublished - Aug 28 2018

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Keywords

  • artificial photosynthesis
  • carbon fixation
  • localized surface plasmon resonance
  • single molecule
  • surface-enhanced Raman scattering

ASJC Scopus subject areas

  • Materials Science(all)
  • Engineering(all)
  • Physics and Astronomy(all)

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