Atomic-Scale Insights into Nickel Exsolution on LaNiO₃ Catalysts via In Situ Electron Microscopy

Using a combination of in situ bulk and surface characterization techniques, we provide atomic-scale insight into the complex surface and bulk dynamics of a LaNiO₃ perovskite material during heating in vacuo. Driven by the outstanding activity LaNiO₃ in the methane dry reforming reaction (DRM), attributable to the decomposition of LaNiO₃ during DRM operation into a Ni//La₂O₃ composite, we reveal the Ni exsolution dynamics both on a local and global scale by in situ electron microscopy, in situ X-ray diffraction and in situ X-ray photoelectron spectroscopy. To reduce the complexity and disentangle thermal from self-activation and reaction-induced effects, we embarked on a heating experiment in vacuo under comparable experimental conditions in all methods. Associated with the Ni exsolution, the remaining perovskite grains suffer a drastic shrinkage of the grain volume and compression of the structure. Ni particles mainly evolve at grain boundaries and stacking faults. Sophisticated structure analysis of the elemental composition by electron-energy loss mapping allows us to disentangle the distribution of the different structures resulting from LaNiO₃ decomposition on a local scale. Important for explaining the DRM activity, our results indicate that most of the Ni moieties are oxidized and that the formation of NiO occurs preferentially at grain edges, resulting from the reaction of the exsolved Ni particles with oxygen released from the perovskite lattice during decomposition via a spillover process from the perovskite to the Ni particles. Correlating electron microscopy and X-ray diffraction data allows us to establish a sequential two-step process in the decomposition of LaNiO₃ via a Ruddlesden-Popper La₂NiO₄ intermediate structure. Exemplified for the archetypical LaNiO₃ perovskite material, our results underscore the importance of focusing on both surface and bulk characterization for a thorough understanding of the catalyst dynamics and set the stage for a generalized concept in the understanding of state-of-the art catalyst materials on an atomic level.