Spin Selection Rule in Single-Site Catalysis of Molecular Oxygen Adsorption on Transition-Metal Phthalocyanines

Development of nonprecious catalysts for O2 reduction reactions based on N4 macrocyclic transition-metal (TM) complexes demands a comprehensive understanding of the microscopic nature of O2 interaction with the central TM atoms. Yet to date, the underlying mechanism that dominates the adsorption ability and thus the reactivity of O2 remains elusive. Here we systematically investigate the adsorption strengths of O2 on the central TM atoms in monolayer and bilayer films of cobalt and iron phthalocyanine molecules supported on the Au(111) surface, using low-temperature scanning tunneling microscopy in combination with first-principles calculations. Comparing the experimental results with the theoretic calculations, we find that spin conservation is a prerequisite in ensuring effective adsorption of O2 on the central TM atoms, in addition to the expectation of the d-band center theory based on the charge degree of freedom of the electrons. We expect this concerted principle of spin and charge to be broadly ap...

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