Probing Molecular-Scale Catalytic Interactions between Oxygen and Cobalt Phthalocyanine Using Tip-Enhanced Raman Spectroscopy

Duc Nguyen, Gyeongwon Kang, Naihao Chiang, Xu Chen, Tamar Seideman, Mark C Hersam, George C Schatz, Richard P. Van Duyne

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

Ultrahigh vacuum tip-enhanced Raman spectroscopy (UHV-TERS) is used to investigate adsorption of molecular oxygen (O2) on cobalt(II) phthalocyanine (CoPc) supported on Ag(111) single crystal surfaces, which is the initial step for the oxygen reduction reaction (ORR) using metal Pc catalysts. Two adsorption configurations are primarily observed, assigned as O2/CoPc/Ag(111) and O/CoPc/Ag(111) based on scanning tunneling microscopy (STM) imaging, TERS, isotopologue substitution, and density functional theory (DFT) calculations. Distinct vibrational features are observed for different adsorption configurations such as the 18O-18O stretching frequency at 1151 cm-1 for O2/CoPc/Ag(111), and Co-16O and Co-18O vibrational frequencies at 661 and 623 cm-1, respectively, for O/CoPc/Ag(111). DFT calculations show vibrational mode coupling of O-O and Co-O vibrations to the Pc ring, resulting in different symmetries of oxygen-related normal modes. This study establishes UHV-TERS as a chemically sensitive tool for probing catalytic systems at the molecular scale.

Original languageEnglish
Pages (from-to)5948-5954
Number of pages7
JournalJournal of the American Chemical Society
Volume140
Issue number18
DOIs
Publication statusPublished - May 9 2018

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Raman Spectrum Analysis
Cobalt
Raman spectroscopy
Oxygen
Adsorption
Ultrahigh vacuum
Vacuum
Density functional theory
Scanning Tunnelling Microscopy
Single crystal surfaces
Molecular oxygen
Scanning tunneling microscopy
Vibrational spectra
Vibration
Stretching
Substitution reactions
Metals
cobalt phthalocyanine
phthalocyanine
Imaging techniques

ASJC Scopus subject areas

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

Cite this

Probing Molecular-Scale Catalytic Interactions between Oxygen and Cobalt Phthalocyanine Using Tip-Enhanced Raman Spectroscopy. / Nguyen, Duc; Kang, Gyeongwon; Chiang, Naihao; Chen, Xu; Seideman, Tamar; Hersam, Mark C; Schatz, George C; Van Duyne, Richard P.

In: Journal of the American Chemical Society, Vol. 140, No. 18, 09.05.2018, p. 5948-5954.

Research output: Contribution to journalArticle

Nguyen, Duc ; Kang, Gyeongwon ; Chiang, Naihao ; Chen, Xu ; Seideman, Tamar ; Hersam, Mark C ; Schatz, George C ; Van Duyne, Richard P. / Probing Molecular-Scale Catalytic Interactions between Oxygen and Cobalt Phthalocyanine Using Tip-Enhanced Raman Spectroscopy. In: Journal of the American Chemical Society. 2018 ; Vol. 140, No. 18. pp. 5948-5954.
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