Two-Dimensional Titanium Dioxide-Surfactant Photoactive Supramolecular Networks: Synthesis, Properties, and Applications for the Conversion of Light Energy.

The desire to harness solar energy to address current global environmental problems led us to investigate two-dimensional (2D) core-shell hybrid photocatalysts in the form of a 2D-TiO2-surfactant, mainly composed of fatty acids. The bulk products, prepared by two slightly different methods, consist of stacked host-guest hybrid sheets held together by van der Waals forces between alkyl carboxylate moieties, favoring the synergistic conjugation of the photophysical properties of the core and the hydrophobicity of the self-assembled surfactant monolayer of the shell. X-ray diffraction and the vibrational characteristics of the products revealed the influence of synthesis strategies on two types of supramolecular aggregates that differ in the core chemical structure, guest conformers of alkyl surfactant tails and type, and the bilayer and monolayer of the structure of nanocomposites. The singular ability of the TiO2 core to anchor carboxylate leads to commensurate hybrids, in contrast to both layered clay and layered double-hydroxide-based ion exchangers which have been previously reported, making them potentially interesting for modeling the role of fatty acids and lipids in bio-systems. The optical properties and photocatalytic activity of the products, mainly in composites with smaller bandgap semiconductors, are qualitatively similar to those of nanostructured TiO2 but improve their photoresponse due to bandgap shifts and the extreme aspect-ratio characteristics of two-dimensional TiO2 confinement. These results could be seen as a proof-of-concept of the potential of these materials to create custom-designed 2D-TiO2-surfactant supramolecular photocatalysts.

ZnO nucleation into trititanate nanotubes by ALD equipment techniques, a new way to functionalize layered metal oxides.

In this contribution, we explore the potential of atomic layer deposition (ALD) techniques for developing new semiconductor metal oxide composites. Specifically, we investigate the functionalization of multi-wall trititanate nanotubes, H2Ti3O7 NTs (sample T1) with zinc oxide employing two different ALD approaches: vapor phase metalation (VPM) using diethylzinc (Zn(C2H5)2, DEZ) as a unique ALD precursor, and multiple pulsed vapor phase infiltration (MPI) using DEZ and water as precursors. We obtained two different types of tubular H2Ti3O7 species containing ZnO in their structures. Multi-wall trititanate nanotubes with ZnO intercalated inside the tube wall sheets were the main products from the VPM infiltration (sample T2). On the other hand, MPI (sample T3) principally leads to single-wall nanotubes with a ZnO hierarchical bi-modal functionalization, thin film coating, and surface decorated with ZnO particles. The products were mainly characterized by electron microscopy, energy dispersive X-ray, powder X-ray diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. An initial evaluation of the optical characteristics of the products demonstrated that they behaved as semiconductors. The IR study revealed the role of water, endogenous and/or exogenous, in determining the structure and properties of the products. The results confirm that ALD is a versatile tool, promising for developing tailor-made semiconductor materials.

Electrochemical Hydrogen Evolution over Hydrothermally Synthesized Re-Doped MoS2 Flower-Like Microspheres.

In this research, we report a simple hydrothermal synthesis to prepare rhenium (Re)- doped MoS2 flower-like microspheres and the tuning of their structural, electronic, and electrocatalytic properties by modulating the insertion of Re. The obtained compounds were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). Structural, morphological, and chemical analyses confirmed the synthesis of poorly crystalline Re-doped MoS2 flower-like microspheres composed of few stacked layers. They exhibit enhanced hydrogen evolution reaction (HER) performance with low overpotential of 210 mV at current density of 10 mA/cm2, with a small Tafel slope of 78 mV/dec. The enhanced catalytic HER performance can be ascribed to activation of MoS2 basal planes and by reduction in charge transfer resistance during HER upon doping.

Fabrication of copper nanoparticles: advances in synthesis, morphology control, and chemical stability.

Metal nanoparticles have attracted great interest particularly because of the size dependence of physical and chemical properties and its enormous technological potential. Although most pioneering advancements refers to gold and silver, more recently there is growing interest in nanoparticles of copper, mostly due to its relatively low cost, which could allow the use of these small metal objects in large-scale nanotechnology applications, for example, antiseptics materials and metallic inks. However, the manufacture of copper nanoparticles stable in air with controlled size and shape has been a major challenge because of the relatively high reactivity of this element. Great efforts in getting the basic knowledge and synthesis know-how has gone into finding better ways to produce particles protected against oxidation and selfaggregation under normal conditions. In this review article, we briefly discuss a number of selected papers and recent patents on procedures and other issues related to the fabrication of copper nanoparticles.

Deposition of laminar TiO2-based nanocomposites on a modified quartz crystal gold surface.

The deposition of hybrid organic-inorganic nanocomposites of titanium dioxide--prepared by hydrolysis of titanium tretraisopropoxide modified through exchanging one of its ligands with a butinoxy-, octiloxy- or phenoxy-group--on a gold surface modified by a monolayer of decanethiol was studied using a Quartz Crystal Microbalance. The depositions, performed from a suspension in alcohol of the nanocomposites, consisting in titanium oxide bilayers hydrophobically functionalized, occurs by a spontaneous process 'layer by layer.' However the amount of deposited mass in a layer as well as the rates of deposition depend on the degree of aggregation of the nanocomposite in the suspension which is in turn determined by nature of the organic ligands.

High-yield preparation of titanium dioxide nanostructures by hydrothermal conditions.

The effect of the neutral surfactant dodecylamine and octadecylamine on the synthesis of TiO2-based nanostructures by the treatment of anatase with NaOH under hydrothermal conditions in the temperature range 120-150 degrees C and different reaction times was investigated. The products analyzed by electron microscopy, X-ray diffraction, FT-IR and elemental analysis contains--depending of the amine, the temperature and the duration of the hydrothermal treatment--spherical and tubular species containing the acid H2Ti3O7. The formation of morphologically almost pure phases constituted by nanospheres and nanotubes were obtained at 130 degrees C after about 30 and 50 h respectively. Using dodecylamine, structurally fragile tubular amine containing nanocomposites are obtained, while in the case of the octadecylamine, notoriously stable purely inorganic nanotubes are formed. The role of the amine in these reactions is discussed.

Low-dimensional, hinged bar-code metal oxide layers and free-standing, ordered organic nanostructures from turbostratic vanadium oxide.

Both low-dimensional bar-coded metal oxide layers, which exhibit molecular hinging, and free-standing organic nanostructures can be obtained from unique nanofibers of vanadium oxide (VO(x)). The nanofibers are successfully synthesized by a simple chemical route using an ethanolic solution of vanadium pentoxide xerogel and dodecanethiol resulting in a double bilayered laminar turbostratic structure. The formation of vanadium oxide nanofibers is observed after hydrothermal treatment of the thiol-intercalated xerogel, resulting in typical lengths in the range 2-6 microm and widths of about 50-500 nm. We observe concomitant hinging of the flexible nanofiber lamina at periodic hinge points in the final product on both the nanoscale and molecular level. Bar-coded nanofibers comprise alternating segments of organic-inorganic (thiols-VO(x)) material and are amenable to segmented, localized metal nanoparticle docking. Under certain conditions free-standing bilayered organic nanostructures are realized.