Physical Transformations of Noble-Metal Nanocrystals upon Thermal Activation

ConspectusThe last two decades have witnessed the successful development of noble-metal nanocrystals with well-controlled properties for a variety of applications in catalysis, plasmonics, electronics, and biomedicine. Most of these nanocrystals are kinetically controlled products greatly deviated from the equilibrium state defined by thermodynamics. When subjected to elevated temperatures, their arrangements of atoms are expected to undergo various physical transformations, inducing changes to the shape, morphology (hollow vs solid), spatial distribution of elements (segregated vs alloyed/intermetallic), internal structure (twinned vs single-crystal), and crystal phase. In order to optimize the performance of these nanocrystals in various applications, there is a pressing need to understand and improve their thermal stability.By integrating in situ heating with transmission electron microscopy or X-ray diffraction, we have investigated the physical transformations of various types of noble-metal nanocrystals in real time. We have also explored the atomistic detail responsible for a physical transformation using first-principles calculations, providing insightful guidance for the development of noble-metal nanocrystals with augmented thermal stability. Specifically, solid nanocrystals were observed to transform into pseudospherical particles favored by thermodynamics by reducing the surface area while eliminating the facets high in surface energy. For nanocrystals of relatively large in size, a single-crystal lattice was more favorable than a twinned structure. When switching to core-shell nanocrystals, the elevation in temperature caused changes to the elemental distribution in addition to shape transformation. The compositional stability of a core-shell nanocrystal was found to be strongly dependent on the shape and thus the type of facet expressed on the surface. For hollow nanocrystals such as nanocages and nanoframes, their thermal stabilities were typically inferior to the solid counterparts, albeit their unique structure and large specific surface area are highly desired in applications such as catalysis. When a metastable crystal structure was involved, phase transition was also observed at a temperature close to that responsible for shape or compositional change. We hope the principles, methodologies, and mechanistic insights presented in this Account will help the readers achieve a good understanding of the physical transformations that are expected to take place in noble-metal nanocrystals when they are subjected to thermal activation. Such an understanding may eventually lead to the development of effective methods for retarding or even preventing some of the transformations.