Theoretical Study on Oxygen Dissociation Reaction on LaSrCoO3
Doped lanthanum cobaltite and its derivatives are used as cathode materials in solid oxide fuel cell (SOFC). For a high catalytic activity, the improvement of properties governing the cathode performance is important. It is generally regarded that one of the important factors is electronic structure of cathode material. It is known that the Co ion in doped lanthanum cobaltite shows three spin states, such as low spin (LS), intermediate spin (IS), and high spin (HS). Hong et al. pointed out that the change of electronic structure due to the difference of spin states affect the formation energy of oxygen vacancy in LaCoO3 bulk system. Although it is expected that the high catalytic materials for oxygen adsorption and dissociation on oxide surface are proposed by the controlling the electronic structure of doped lanthanum cobaltite, the effect of electronic structure due to the difference of spin states of Co ion is unclear for the surface reactions on doped lanthanum cobaltite. In this study, we analyzed the stability of oxygen vacancy and surface reaction of oxygen under the different spin states of Co ion in Sr doped LaCoO3by using density functional theory (DFT) calculation.
We used LaSrO-terminated (001) surface of cubic LaSrCoO3 crystal structure. Half of La atoms were substituted by Sr atoms in LaO layers to analyze the effect of segregation of Sr in La6Sr6Co8O28 slab model. GGA-PBE with PAW potentials were applied with cutoff energy of 600 eV and 2x2x1 k-points. The initial spin configuration was constrained, such as LS, IS, and HS states, to obtain the different electronic structures. All DFT calculations were performed by using VASP.
Results and Discussion
We first analyzed the oxygen vacancy formation energy on the surface of La6Sr6Co8O28. The vacancy formation energies of one oxygen on surface under the LS, IS, and HS states were 0.92, 1.03, and 0.95 eV, respectively. The vacancy formation energies of two oxygen on surface under the LS, IS, and HS states were 3.27, 2.36, and 1.90 eV, respectively. The oxygen vacancy formation became unstable when the number of oxygen vacancy increases in all spin states. The oxygen vacancy formation energy for HS was the smallest compared with LS and IS states for two oxygen vacancy systems. We found that the difference of spin state of Co ion affects the oxygen vacancy formation energy on surface of LaSrCoO3. In addition, we analyzed the stability of oxygen vacancy under the different Sr configurations to understand the effect Sr segregation. Details are discussed in the presentation.
The activities of INAMORI Frontier Research Center are supported by KYOCERA Corporation. All calculations are performed on the HA8000 computer systems in Research Institute for Information Technology, Kyushu University.
 W. T. Hong, M. Gadre, Y. -L. Lee, M. D. Biegalski, H. M. Christen, D. Morgan, and Y. Shao-Horn, J. Phys. Chem. Lett., 4, 2493 (2013).