Tunable physics through coordination chemistry: formation on oxide surface of Ti and Al chelates with 3-hydroxyflavone capable of electron injection and light emission.

The optoelectronic features of 3-hydroxyflavone (3HF) self-assembled on the surface of an n-type semiconducting metal oxide (TiO2) and an insulator (Al2O3) are herein investigated. 3HF molecules use the coordinatively unsaturated metal ions present on the oxide surface to form metal complexes, which exhibit different behaviors upon light irradiation, depending on the nature of the metal ion. Specifically, we show that the photoluminescence of the surface species can be modulated according to the chemical properties of the complex (i.e. the binding metal ion), resulting in solid-state emitters in a high quantum yield (about 15%). Furthermore, photoinduced charge injection can be promoted or inhibited, providing a multifunctional hybrid system.

Solvent-dependent termination, size and stability in polyynes synthesized via laser ablation in liquids.

In recent years there has been growing interest in sp-carbon chains as possible novel nanostructures. An example of sp-carbon chains is the so-called polyyne, characterized by the alternation of single and triple bonds that can be synthesized via pulsed laser ablation in liquid (PLAL) of a graphite target. In this work, by using different solvents in the PLAL process, e.g. water, acetonitrile, methanol, ethanol, and isopropanol, we systematically investigated the role of the solvent in polyyne synthesis and stability, and discussed the possible formation mechanisms. The presence of methyl- and cyano-groups in the solutions influences the termination of polyynes, allowing the detection, of hydrogen-capped polyynes up to H-C22-H, methyl-capped polyynes up to H-C18-CH3 and cyanopolyynes up to H-C12-CN. The assignment of each species was performed via UV-vis spectroscopy and supported by density functional theory simulations of vibronic spectra. In addition, surface-enhanced Raman spectroscopy allowed to highlight the differences in the shape and positions of the characteristic Raman bands of the size-selected polyynes with different terminations (hydrogen, methyl and cyano groups). The stability in time of each polyyne was investigated by evaluating the chromatographic peak area, and the effect of size, terminations and solvents on polyyne stability was individuated.

Synergistic Effects of Active Sites' Nature and Hydrophilicity on the Oxygen Reduction Reaction Activity of Pt-Free Catalysts.

This work highlights the importance of the hydrophilicity of a catalyst's active sites on an oxygen reduction reaction (ORR) through an electrochemical and physico-chemical study on catalysts based on nitrogen-modified carbon doped with different metals (Fe, Cu, and a mixture of them). BET, X-ray Powder Diffraction (XRPD), micro-Raman, X-ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscopy (SEM), Scanning Transmission Electron Microscopy (STEM), and hydrophilicity measurements were performed. All synthesized catalysts are characterized not only by a porous structure, with the porosity distribution centered in the mesoporosity range, but also by the presence of carbon nanostructures. In iron-doped materials, these nanostructures are bamboo-like structures typical of nitrogen carbon nanotubes, which are better organized, in a larger amount, and longer than those in the copper-doped material. Electrochemical ORR results highlight that the presence of iron and nitrogen carbon nanotubes is beneficial to the electroactivity of these materials, but also that the hydrophilicity of the active site is an important parameter affecting electrocatalytic properties. The most active material contains a mixture of Fe and Cu.

Multiscale effect of hierarchical self-assembled nanostructures on superhydrophobic surface.

In this work, we describe self-assembled surfaces with a peculiar multiscale organization, from the nanoscale to the microscale, exhibiting the Cassie-Baxter wetting regime with extremely low water adhesion: floating drops regime with roll-off angles < 5°. These surfaces comprise bundles of hierarchical, quasi-one-dimensional (1D) TiO2 nanostructures functionalized with a fluorinated molecule (PFNA). While the hierarchical nanostructures are the result of a gas-phase self-assembly process, their bundles are the result of the capillary forces acting between them when the PFNA solvent evaporates. Nanometric features are found to influence the hydrophobic behavior of the surface, which is enhanced by the micrometric structures up to the achievement of the superhydrophobic Cassie-Baxter state (contact angle (CA) ≫ 150°). Thanks to their high total and diffuse transmittance and their self-cleaning properties, these surfaces could be interesting for several applications such as smart windows and photovoltaics where light management and surface cleanliness play a crucial role. Moreover, the multiscale analysis performed in this work contributes to the understanding of the basic mechanisms behind extreme wetting behaviors.