Substitution of lanthanum by strontium (Sr) in the A-site of cobalt-containing perovskites can greatly promote oxygen surface exchange kinetics at elevated temperatures. Little is known about the effect of A-site substitution on the oxygen electrocatalysis of Ruddlesden-Popper (RP) oxides. In this study, we report, for the first time, the growth and oxygen surface exchange kinetics of La2-xSrxNiO 4±δ (LSNO, 0.0 ≤ xSr ≤ 1.0) thin films grown on (001)cubic-Y2O3-stabilized ZrO 2 (YSZ) by pulsed laser deposition. High-resolution X-ray diffraction analysis revealed that the LSNO film orientation was changed gradually from the (100)tetra. (in-plane) to the (001)tetra. (out-of-plane) orientation in the RP structure with increasing Sr from La2NiO 4+δ (xSr = 0) to LaSrNiO4±δ (xSr = 1.0). Such a change in the LSNO film orientation was accompanied by reduction in the oxygen surface exchange kinetics by two orders of magnitude as shown from electrochemical impedance spectroscopy results. Density functional theory (DFT) calculations showed that Sr substitution could stabilize the (001)tetra. surface relative to the (100) tetra. surface and both Sr substitution and increasing (001) tetra. surface could greatly weaken adsorption of molecular oxygen in the La-La bridge sites in the RP structure, which can reduce oxygen surface exchange kinetics. This journal is © the Partner Organisations 2014.
Bibliographical noteKAUST Repository Item: Exported on 2020-10-01
Acknowledgements: This work was supported in part by DOE (SISGR DESC0002633) and King Abdullah University of Science and Technology. The authors would like to thank the King Fahd University of Petroleum and Minerals in Dharam, Saudi Arabia, for funding the research reported in this paper through the Center for Clean Water and Clean Energy at MIT and KFUPM. Funding for D. Morgan and partial support for Y.-L. Lee provided by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under award number DESC0001284. This work also benefitted from the use of the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation grant number OCI-1053575. PLD was conducted at the Center for Nanophase Materials Sciences, which is sponsored at Oak Ridge National Laboratory by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy.
This publication acknowledges KAUST support, but has no KAUST affiliated authors.