Finding Correlations of the Oxygen Reduction Reaction Activity of Transition Metal Catalysts with Parameters Obtained from Quantum Mechanics

To facilitate a less empirical approach to developing improved catalysts, it is important to correlate catalytic performance to surrogate properties that can be measured or predicted accurately and quickly, allowing experimental synthesis and testing of catalysts to focus on the most promising cases. Particularly hopeful is correlating catalysis performance to the electronic density of states (DOS). Indeed, there has been success in using just the center of the d-electron density, which in some cases correlates linearly with oxygen atom chemisorption energy, leading to a volcano plot for catalytic performance versus “d-band center”. To test such concepts we calculated the barriers and binding energies for the various reactions and intermediates involved in the oxygen reduction reaction (ORR) for all 12 transition metals in groups 8–11 (Fe–Cu columns). Our results show that the oxygen binding energy can serve as a useful parameter in describing the catalytic activity for pure metals, but it does not necessarily correlate with the d-band center. In addition, we find that the d-band center depends substantially on the calculation method or the experimental setup, making it a much less reliable indicator for ORR activity than the oxygen binding energy. We further examine several surfaces of the same pure metals to evaluate how the d-band center and oxygen binding energy depend on the surface