TY - JOUR
T1 - Molecular-Scale Mechanistic Investigation of Oxygen Dissociation and Adsorption on Metal Surface-Supported Cobalt Phthalocyanine
AU - Nguyen, Duc
AU - Kang, Gyeongwon
AU - Hersam, Mark C.
AU - Schatz, George C.
AU - Van Duyne, Richard P.
N1 - Funding Information:
D.N., G.K., 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. 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. M.C.H. acknowledges support from the National Science Foundation Materials Research Science and Engineering Center (NSF Grant DMR-1121262).
Publisher Copyright:
Copyright © 2019 American Chemical Society.
PY - 2019/6/28
Y1 - 2019/6/28
N2 - Ultrahigh vacuum scanning tunneling microscopy and density functional theory are used to investigate adsorption of oxygen on cobalt phthalocyanine (CoPc), a promising nonprecious metal oxygen reduction catalyst, supported on Ag(111), Cu(111), and Au(111) surfaces at the molecular scale. Four distinct molecular and atomic oxygen adsorption configurations are observed for CoPc supported on Ag(111) surfaces, which are assigned as O2/CoPc/Ag(111), O/CoPc/Ag(111), CoPc/(O)2/Ag(111), and (O)2/CoPc/Ag(111). In contrast, no oxygen adsorption is observed for CoPc supported on Cu(111) and Au(111) surfaces. The results show that for Ag(111), atomic O that is predominantly catalytically produced from the dissociation of molecular O2 at metal surface step edges is responsible for the observed adsorption configurations. However, Cu(111) binds atomic O too strongly, and Au(111) does not produce atomic O. These results show the active role of the supporting metal surface in facilitating oxygen adsorption on CoPc.
AB - Ultrahigh vacuum scanning tunneling microscopy and density functional theory are used to investigate adsorption of oxygen on cobalt phthalocyanine (CoPc), a promising nonprecious metal oxygen reduction catalyst, supported on Ag(111), Cu(111), and Au(111) surfaces at the molecular scale. Four distinct molecular and atomic oxygen adsorption configurations are observed for CoPc supported on Ag(111) surfaces, which are assigned as O2/CoPc/Ag(111), O/CoPc/Ag(111), CoPc/(O)2/Ag(111), and (O)2/CoPc/Ag(111). In contrast, no oxygen adsorption is observed for CoPc supported on Cu(111) and Au(111) surfaces. The results show that for Ag(111), atomic O that is predominantly catalytically produced from the dissociation of molecular O2 at metal surface step edges is responsible for the observed adsorption configurations. However, Cu(111) binds atomic O too strongly, and Au(111) does not produce atomic O. These results show the active role of the supporting metal surface in facilitating oxygen adsorption on CoPc.
UR - http://www.scopus.com/inward/record.url?scp=85069847665&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85069847665&partnerID=8YFLogxK
U2 - 10.1021/acs.jpclett.9b00926
DO - 10.1021/acs.jpclett.9b00926
M3 - Article
C2 - 31251623
AN - SCOPUS:85069847665
SN - 1948-7185
VL - 10
SP - 3966
EP - 3971
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 14
ER -