Shape-and phase-controlled ZnSe nanocrystals are synthesized in hot mixtures of long-chain alkylamines and alkylphosphines. The variation in the rate of precursor addition, down to low and controlled levels, allows the nucleation, as well as the growth of the nanocrystals, to switch between the wurtzite and the zinc blend structures. Such a level of control leads to a variety of shapes, from spheres to rods to threedimensional structures formed by rod sections interconnected through branching points. The temperatureand time-dependence of the chemical potentials for the monomer species in solution are the most relevant parameters involved in the growth mechanism.

A novel colloidal approach toward semiconductor/metal nanocomposites is presented. Organic-soluble anatase TiO(2) nanorods are used for the first time to stabilize Ag nanoparticles in optically clear nonpolar solutions in the absence of specific ligands for silver. Metallic silver is generated upon UV illumination of deaerated TiO(2) solutions containing AgNO(3). The Ag nanoparticles can be obtained in different size-morphological regimes as a function of the irradiation time, due to light-induced photofragmentation and ripening processes. A mechanism for the colloidal stabilization of the silver nanoparticles is tentatively suggested, which regards the TiO(2) nanorods as inorganic stabilizers, thus acting in the same manner as conventional surfactant molecules. The proposed photocatalytic approach offers a convenient method for producing TiO(2)/Ag nanocomposite systems with a certain control over the metal particle size without the use of surfactants and/or additives. Stable colloidal TiO(2)-nanorod-stabilized Ag nanoparticles can be potentially available for a number of applications that require "clean" metal surfaces, such as homogeneous organic catalysis, photocatalysis, and sensing devices.

Asymmetric binary nanocrystals (BNCs), comprising one c-axis elongated anatase TiO2 section and one gamma-Fe2O3 spherical domain attached together, are synthesized by heterogeneous nucleation of iron oxide onto the longitudinal facets of TiO2 nanorods in a ternary surfactant mixture. The topologically controlled composition of the BNCs is ascertained by a combination of powder X-ray diffraction, Raman and Mössbauer spectroscopy, high-angle annular dark-field imaging, and high-resolution transmission electron microscopy lattice fringe mapping, while their size-dependent magnetic behavior is demonstrated by ac susceptibility measurements. The heteroepitaxial growth proceeds through a mechanism never observed before for colloidal nanoheterostructures: the two domains share a restricted and locally curved junction region, which accommodates efficiently the interfacial strain and retards the formation of misfit dislocations. It is believed that these BNCs, which combine the properties of two technologically relevant oxide materials, can pave the way to reinforced applications in several fields of nanoscience, such as in photocatalysis, in malignant cell treatments, and in nanocrystal assembly.

The photocatalytic performance of anatase TiO 2 nanorod-stabilized Ag nanoparticles has been investigated during the reductive bleaching of a model dye, Uniblue A (UBA), in homogeneous organic solutions. The activity of the TiO 2 /Ag nanocomposite has been found to vary continuously during the course of photocatalysis, following a concomitant light-induced modification of the metal nanoparticle size and size distribution. The direct involvement of the metal particles in mediating electron transfer between photoexcited TiO 2 and the target UBA is explained on the basis of the size-dependent redox properties of the metal nanoparticles. The present results can be useful in the design of new composite materials with well-tailored photocatalytic properties and long-term stability.

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The role of Ag+ ions in the ultraviolet-driven photochemical synthesis of Au nanorods (NRs) in aqueous surfactant mixtures has been investigated in order to elucidate the mechanism that drives anisotropic nanoparticle growth. The samples, grown in the presence of varying amounts of Ag+ ions for scheduled irradiation times, have been characterized by ultraviolet−visible−near infrared (UV−vis−NIR) absorption spectroscopy, analytical transmission electron microscopy (ATEM), inductively coupled plasma atomic emission spectroscopy (ICP-AES), and extended X-ray absorption fine structure (EXAFS) measurements. Moreover, the time evolution of size and shape distribution has been investigated by statistical analysis of the relevant TEM data. EXAFS measurements at the Ag K-edge have unambiguously disclosed the presence of Ag species in the final product, identifying their chemical state as well as the most probable lattice environment around them with a reasonably high level of confidence. The extensive sample knowledge gained by the combination of spectroscopic, structural, and morphological measurements has provided reliable information regarding the most relevant processes underlying the Ag+-assisted formation of Au NRs by the photochemical route. An induction period prior to occurrence of fast nanoparticle nucleation has been identified, which has been correlated to the slow accumulation of a critical concentration of Au(I)−surfactant species from reduction of their Au(III) parent precursors. The role played by Ag in directing Au growth toward the formation of NRs has been clarified through demonstration of preferential adsorption of zerovalent Ag species on {110} facets of the growing Au nanoparticles, which can be therefore responsible for restricting crystal development along the relevant crystallographic directions