We provide general descriptions regarding the structure–stability correlations of iridium-based complex-oxide catalysts for oxygen evolution reaction in acid media.

No abstract

A substantial amount of interest has been focused on AB O 3 -type perovskite oxides over the past decade as oxygen electrocatalysts. Despite many studies on various compositions, the correlation between the structure of the oxygen octahedra and electrocatalytic property has been overlooked, and there accordingly have been a very limited number of attempts regarding control of atomistic structure. Utilizing epitaxial Ln NiO 3 ( Ln = La, Pr, Nd) thin films, here we demonstrate that simple electrochemical exchange of Fe in the surface region with several-unit-cell thickness is notably effective to boost the catalytic activity for the oxygen evolution reaction by different orders of magnitude. Furthermore, we directly establish that strong distortion of oxygen octahedra at the angstrom scale is readily induced during the Fe exchange, and that this structural perturbation permits easier charge transfer. The findings suggest that structural alteration can be an efficient approach to achieve exceptional electrocatalysis in crystalline oxides.

Atomic-scale direct probing of active sites and subsequent elucidation of the structure-activity relationship are important issues involving oxide-based electrocatalysts to achieve better electrochemical conversion efficiency. By generating Ruddlesden-Popper (RP) two-dimensional homologous faults via simple control of the cation nonstoichiometry in LaNiO thin films, we demonstrate that strong tetragonal distortion of [NiO] octahedra is induced by more than 20% elongation of Ni-O bonds in the faults. In addition to direct visualization of the elongation by scanning transmission electron microscopy, we identify that the distorted [NiO] octahedra in the faults show considerably higher electrocatalytic activities than other surface sites during the electrochemical oxygen evolution reaction. This unequivocal evidence of the octahedral distortion and its impact on electrocatalysis in LaNiO suggests that the formation of RP-type faults can provide an efficient way to control the octahedral geometry and thereby remarkably enhance the oxygen catalytic performance of perovskite oxides.

Using spinel-type Li(Mn(1.5)Ni(0.5) )O4 with two different cations, Mn and Ni, in the oxygen octahedra as a model system, we show that a cation ordering transition takes place through the formation of Frenkel-type point defects. A series of experimental results based on atomic-scale observations and in situ powder diffractions along with ab initio calculations consistently support such defect-mediated transition behavior. In addition to providing a precise suggestion of the intermediate transient states and the resulting kinetic pathway during the transition between two phases, our findings emphasize the significant role of point defects in ordering transformation of complex oxides.