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Abstract

The shape of platinum and gold nanoparticles (NPs) synthesized via inverse micelle encapsulation and supported on TiO₂(110) has been resolved by scanning tunneling microscopy. Annealing these systems at high temperature (∼1000 °C) and subsequent cooling to room temperature produced ordered arrays of well-separated three-dimensional faceted NPs in their equilibrium state. The observed shapes differ from the kinetically limited shapes of conventional physical vapor deposited NPs, which normally form two-dimensional flat islands upon annealing at elevated temperatures. The initial NP volume was found to provide a means to control the final NP shape. Despite the liquid-phase ex situ synthesis of the micellar particles, the in situ removal of the encapsulating ligands and subsequent annealing consistently lead to the development of a well-defined epitaxial relationship of the metal NPs with the oxide support. The observed epitaxial relationships could be explained in terms of the best overlap between the interfacial Pt (or Au) and TiO₂ lattices. In most cases, the ratio of {100}/{111} facets obtained for the NP shapes resolved clearly deviates from that of conventional bulklike Wulff structures.