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ABSTRACT Perovskite oxides doped with transition metals play a critical role in several contemporary applications, such as electro‐ and photocatalysis and the synthesis of coke‐ and sintering‐resistant catalysts. In this study, we present a systematic investigation of the doping preferences and surface segregation trends of 4d transition metals in (A = Ca, Sr, Ba) perovskites using first‐principles density functional theory (DFT) calculations. We further consider the influence of different facets and terminations such as (001)‐AO/, (110)‐ABO/, and (111)‐/B, and the application of tensile and compressive strain on the segregation behavior of these dopants. Results indicate that doping and segregation behaviors depend strongly on the exposed facet and applied strain, but less so on the host perovskite oxide. Additionally, we find that early transition metals strongly prefer bulk and subsurface doping, while later metals, beginning with Ru, segregate to the surface. We rationalize and corroborate the computed trends against a comprehensive set of previously published experimental data, highlighting the critical role of facet, termination, and strain in determining doping and segregation behavior. The results serve as a suitable starting point for designing perovskite systems with tailored properties.
Alayyoub et al. (Sun,) studied this question.