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

doi:10.1021/jacs.8b01154

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^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

78 Scopus citations

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 language	English (US)
Pages (from-to)	5948-5954
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	140
Issue number	18
DOIs	https://doi.org/10.1021/jacs.8b01154
State	Published - May 9 2018

Funding

D.N., N.C, G.C.S, and R.P.V.D. acknowledge support from the National Science Foundation Center for Chemical Innovation dedicated to Chemistry at the Space-Time Limit (CaSTL) Grant CHE-1414466. D.N., G.K., X.C., G.C.S, and R.P.V.D. acknowledge support from the Air Force Office of Scientific Research MURI (FA9550-14-1-0003). G.K. and G.C.S. acknowledge support from Northwestern University Information Technology (NUIT) team and the Center for Nanoscale Materials (CNM) at Argonne National Laboratory for the computational resources. N.C., T.S., M.C.H., and R.P.V.D. acknowledge support from the National Science Foundation Materials Research Science and Engineering Center (NSF Grant DMR-1121262).

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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

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.",

author = "Duc Nguyen and Gyeongwon Kang and Naihao Chiang and Xu Chen and Tamar Seideman and Hersam, \{Mark C.\} and Schatz, \{George C.\} and \{Van Duyne\}, \{Richard P.\}",

note = "Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

year = "2018",

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doi = "10.1021/jacs.8b01154",

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AU - Chen, Xu

AU - Seideman, Tamar

AU - Hersam, Mark C.

AU - Schatz, George C.

AU - Van Duyne, Richard P.

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AB - 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.

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

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