Ultrathin ordered titanium oxide films on Pt(111) surface are prepared by reactive evaporation of Ti in oxygen. By varying the Ti dose and the annealing conditions (i.e., temperature and oxygen pressure), six different long-range ordered phases are obtained. They are characterized by means of low-energy electron diffraction (LEED), X-ray photoemission spectroscopy (XPS), and scanning tunneling microscopy (STM). By careful optimization of the preparative parameters, we find conditions where predominantly single phases of TiO(x), revealing distinct LEED pattern and STM images, are produced. XPS binding energy and photoelectron diffraction (XPD) data indicate that all the phases, except one (the stoichiometric rect-TiO2), are one monolayer thick and composed of a Ti-O bilayer with interfacial Ti. Atomically resolved STM images confirm that these TiO(x) phases wet the Pt surface, in contrast to rect-TiO2. This indicates their interface stabilization. At a low Ti dose (0.4 monolayer equivalents, MLE), an incommensurate kagomé-like low-density phase (k-TiO(x) phase) is observed where hexagons are sharing their vertexes. At a higher Ti dose (0.8 MLE), two denser phases are found, both characterized by a zigzag motif (z- and z'-TiO(x) phases), but with distinct rectangular unit cells. Among them, z'-TiO(x), which is obtained by annealing in ultrahigh vacuum (UHV), shows a larger unit cell. When the postannealing of the 0.8 MLE deposit is carried out at high temperatures and high oxygen partial pressures, the incommensurate nonwetting, fully oxidized rect-TiO2 is found The symmetry and lattice dimensions are almost identical with rect-VO2, observed in the system VO(x)/Pd(111). At a higher coverage (1.2 MLE), two commensurate hexagonal phases are formed, namely the w- [(square root(43) x square root(43)) R 7.6 degrees] and w'-TiO(x) phase [(7 x 7) R 21.8 degrees]. They show wagon-wheel-like structures and have slightly different lattice dimensions. Larger Ti deposits produce TiO2 nanoclusters on top of the different monolayer films, as supported both by XPS and STM data. Besides the formation of TiO(x) surfaces phases, wormlike features are found on the bare parts of the substrate by STM. We suggest that these structures, probably multilayer disordered TiO2, represent growth precursors of the ordered phases. Our results on the different nanostructures are compared with literature data on similar systems, e.g., VO(x)/Pd(111), VO(x)/Rh(111), TiO(x)/Pd(111), TiO(x)/Pt(111), and TiO(x)/Ru(0001). Similar and distinct features are observed in the TiO(x)/Pt(111) case, which may be related to the different chemical natures of the overlayer and of the substrate.

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Gold nanoparticles are synthesized by laser ablation of a gold plate in toluene. The nanoparticles do not show their characteristic surface plasmon absorption (SPA) and are found to be included in a graphitic matrix. The absence of this absorption is found to derive from the presence of the matrix which prevents the growth of large nanoparticles and covers them, suppressing the SPA according to the Mie model for core@shell particles. It is possible to recover the nanoparticle SPA by oxidizing the carbon matrix, obtaining, therefore, some control on the activity of this absorption.

The structure of well-ordered reduced TiOx nanolayers (NLs) on Pt(111), prepared by reactive evaporation of Ti in an oxygen background and postannealed in different conditions, is discussed on the basis of experimental and theoretical data. All of the observed NLs are formed by a wetting 2D Ti−O bilayer where the Ti atoms are at the interface and the O atoms form the topmost layer. Different structures and stoichiometries depend on the actual Ti coverage and on the conditions of the postannealing. They represent the final products of a self-assembling process where the Ti atoms tend to organize in pseudoepitaxial regions, whereas the O atoms in the topmost layer (more abundant due to stoichiometry constraints) solve the crowding problem by creating pseudoepitaxial regions that exhibit dislocation lines and alternate with regions where Ti vacancies (defects or holes) occur. Given the inherent similarity among such reduced phases, as confirmed by an analysis of their electronic structure, it turns out that subtle effects are at the origin of the large variety of possible structures and that kinetic effects during their synthesis can play a role in driving toward a specific phase