Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 139, Issue 20, Pages -Publisher
AMER INST PHYSICS
DOI: 10.1063/1.4832696
Keywords
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Funding
- Chemical Sciences Research Programs, Office of Basic Energy Sciences, U.S. Department of Energy [DE-FG02-09ER16093]
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Oxygen adsorption energy is directly relevant to the catalytic activity of electrocatalysts for oxygen reduction reaction (ORR). In this study, we established the correlation between the O-2 adsorption energy and the electronic structure of transition metal macrocyclic complexes which exhibit activity for ORR. To this end, we have predicted the molecular and electronic structures of a series of transition metal macrocyclic complexes with planar N-4 chelation, as well as the molecular and electronic structures for the O-2 adsorption on these macrocyclic molecules, using the density functional theory calculation method. We found that the calculated adsorption energy of O-2 on the transition metal macrocyclic complexes was linearly related to the average position (relative to the lowest unoccupied molecular orbital of the macrocyclic complexes) of the non-bonding d orbitals (d(z2), d(xy), d(xz), and d(yz)) which belong to the central transition metal atom. Importantly, our results suggest that varying the energy level of the non-bonding d orbitals through changing the central transition metal atom and/or peripheral ligand groups could be an effective way to tuning their O-2 adsorption energy for enhancing the ORR activity of transition metal macrocyclic complex catalysts. (C) 2013 AIP Publishing LLC.
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