Molecular-Scale Mechanistic Investigation of Oxygen Dissociation and Adsorption on Metal Surface-Supported Cobalt Phthalocyanine
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.