ABSTRACT
Single and multi-atoms supported on oxide substrates ultimately increase the efficiency of noble metal atom use, and moreover, catalytic activity and selectivity are also improved substantially. However, single and multi-atoms are unstable under catalytic conditions, and these metal atoms spontaneously aggregate and grow into nanoparticles. Catalytic performance is strongly related to local atomic configurations, and hence, it is essential to determine the three-dimensional (3D) atomic structures of multi-atoms on the substrate and their structural dynamics. Here, we show the real-time tracking of the 3D structural evolution of a Pt trimer on TiO2 (110) substrate at a high temperature, using high-spatiotemporal-resolution scanning transmission electron microscopy, where sub-angstrom spatial resolution is maintained, while the temporal resolution reaches 40 milliseconds. With the aid of prior structural knowledge of a Pt trimer for 3D reconstruction, the present method could open the way to characterize in situ atomic-scale structural dynamics, especially meta-stable structural transition.
ABSTRACT
Grain-boundary atomic structures of crystalline materials have long been believed to be commensurate with the crystal periodicity of the adjacent crystals. In the present study, we experimentally observed a Σ9 grain-boundary atomic structure of a bcc crystal (Fe-3%Si). It is found that the Σ9 grain-boundary structure is largely reconstructed and forms a dense packing of icosahedral clusters in its core. Combining with the detailed theoretical calculations, the Σ9 grain-boundary atomic structure is discovered to be incommensurate with the adjacent crystal structures. The present findings shed new light on the study of stable grain-boundary atomic structures in crystalline materials.
ABSTRACT
Impurity doping is a conventional but one of the most effective ways to control the functional properties of materials. In insulating materials, the dopant solubility limit is considerably low in general, and the dopants often segregate to grain boundaries (GBs) in polycrystals, which significantly alter their entire properties. However, detailed mechanisms on how dopant atoms form structures at GBs and change their properties remain a matter of conjecture. Here, we show GB structural transformation in α-Al2O3 induced by co-segregation of Ca and Si aliovalent dopants using atomic-resolution scanning transmission electron microscopy combined with density functional theory calculations. To accommodate large-sized Ca ions at the GB core, the pristine GB atomic structure is transformed into a new GB structure with larger free volumes. Moreover, the Si and Ca dopants form a chemically ordered structure, and the charge compensation is achieved within the narrow GB core region rather than forming broader space charge layers. Our findings give an insight into GB engineering by utilizing aliovalent co-segregation.
