Daniela Meroni

Wettability of bare and fluorinated silanes: A combined approach based on surface free energy evaluations and dipole moment calculations

The assessment of the surface free energy (SFE) of a material permits to control and predict a large number of physicochemical properties of a solid surface and its reactivity. Here, the surface energies of a series of bare and fluorinated silanes are determined by means of different semi-empirical models on the grounds of contact angle determinations for different solvents. Literature data are also considered in order to produce a series of films with increasing SFE. Wetting envelopes (WE) are obtained for the various surfaces in order to predict the wettability of the films by numerous commonly employed solvents. The polar and disperse components of the surface energies are obtained by the Owens-Wendt-Rabel-Kaelbe (OWRK) method; the values of the polar components are compared with gas-phase dipole moments obtained by theoretical calculations employing semi-empirical Hamiltonians. The sequences of the polar components of the SFE and of the calculated dipole moments for the different molecules are strictly the same. The interplay between theoretical and experimental approaches proves efficient in predicting the behavior of different systems and it could be employed in tuning the SFE of a solid surface with respect to its final applications.

Electrochemically assisted deposition of transparent, mechanically robust TiO2 films for advanced applications

In recent years, titanium dioxide has received ever growing interest, thanks to its promising applications in numerous fields such as environmental remediation, H2 generation and photovoltaics. Here, transparent and mechanically robust TiO2 films are deposited by a simple and inexpensive electrochemically assisted procedure on various kinds of substrates, both conductive and nonconductive (e.g., glass slides or different metal laminas with variable surface roughness). The obtained films are uniform, crack-free and exhibit excellent chemical, mechanical, and electrochemical robustness. The obtained layers are compared to films prepared by a routine preparation technique, such as dip coating, showing much better morphological, optical, and conductive properties. The photo-activity of TiO2 can be exploited to obtain transparent spectroelectrochemical systems and to control the wetting features of the surface. Applications concerning the modulation of the wettability are presented with respect to both the antifogging and antistain properties. The photoelectrochemical properties of TiO2 films are exploited to activate a photoelectrochemical polymerization of polypyrrole onto an unconductive support. These materials are promising for numerous applications such as smart windows, antifogging mirrors, solar cells, and optically transparent electrodes.

A Close Look at the Structure of the TiO2-APTES Interface in Hybrid Nanomaterials and Its Degradation Pathway: An Experimental and Theoretical Study

The surface functionalization of TiO2-based materials with alkylsilanes is attractive in several cutting-edge applications, such as photovoltaics, sensors, and nanocarriers for the controlled release of bioactive molecules. (3-Aminopropyl)triethoxysilane (APTES) is able to self-assemble to form monolayers on TiO2 surfaces, but its adsorption geometry and solar-induced photodegradation pathways are not well understood. We here employ advanced experimental (XPS, NEXAFS, AFM, HR-TEM, and FT-IR) and theoretical (plane-wave DFT) tools to investigate the preferential interaction mode of APTES on anatase TiO2. We demonstrate that monomeric APTES chemisorption should proceed through covalent Si–O–Ti bonds. Although dimerization of the silane through Si–O–Si bonds is possible, further polymerization on the surface is scarcely probable. Terminal amino groups are expected to be partially involved in strong charge-assisted hydrogen bonds with surface hydroxyl groups of TiO2, resulting in a reduced propensity to react with other species. Solar-induced mineralization proceeds through preferential cleavage of the alkyl groups, leading to the rapid loss of the terminal NH2 moieties, whereas the Si-bearing head of APTES undergoes slower oxidation and remains bound to the surface. The suitability of employing the silane as a linker with other chemical species is discussed in the context of controlled degradation of APTES monolayers for drug release and surface patterning.

Engineered organic/inorganic hybrids for superhydrophobic coatings by wet and vapour procedures

Siloxane/oxide hybrids have attracted growing attention thanks to their ability to modulate the surface energy, wettability, or self-lubricity of a material. Here, we compare two functionalisation procedures (chemical vapour deposition and wet impregnation) on substrate films composed by preformed oxide particles. Three kinds of particles, characterised by different natures (SiO2 and TiO2) and average particle size, were studied to highlight possible effects related to the chemical and morphological state of the substrate surface. Morphological characterisations were carried out using dynamic light scattering and scanning electron microscopy, while the structure of the hydrophobing layer was studied by combining Fourier transform infrared spectroscopy and solid-state nuclear magnetic resonance. The degree of functionalisation and the features of the siloxane layer vary significantly among the adopted oxides and functionalisation methods. The wettability features of the different hybrids closely mirror the results of the spectroscopic characterisations, giving rise to either Lotus leaf or patch-wise hydrophobic systems depending on the adopted conditions.

Electrochemical sensors cleaned by light: a proof of concept for on site applications towards integrated monitoring systems

The potential for on site applications of a SiO2–Ag NPs–TiO2 self-cleaning electrode was demonstrated. Dopamine was used both as the analyte and the fouling agent. Three different UV lamps (a powerful lamp (45 mW cm−2) for photocatalysis, a TLC lamp and a commercial LED torch) were studied. After fouling, total recovery of the electroanalytical performances was achieved upon a short irradiation performed directly in the solution of interest.

Sol–Gel Synthesis of CaTiO3:Pr3+ Red Phosphors: Tailoring the Synthetic Parameters for Luminescent and Afterglow Applications

Two sol–gel synthetic routes for the preparation of CaTiO3:Pr3+ red emitting phosphors were compared, with the aim of producing nanostructured materials with tailored luminescence/afterglow properties. The effect of the synthetic parameters, such as the addition of a stabilizer and calcination temperature, on the structural, morphological, and optical properties was investigated. The desired perovskite phase was obtained at a calcination temperature of 800 °C or higher. Although the use of acetic acid as the chelating agent leads to micrometric particles with heterogeneous composition, the presence of hydroxypropylcellulose (HPC) results in smaller, less aggregated particles as well as in a high phase purity. At the highest HPC content, surface Ca-rich impurities were detected, although no segregated Ca-rich phases were detectable by X-ray powder diffraction analyses. Luminescence properties were found to be positively related to the phase purity of the oxide, with the highest quantum yields at temperatures equal to or higher than 1000 °C. On the contrary, persistent luminescence properties were highest at intermediate calcination temperatures and for samples synthesized with acetic acid. Overall, a notable role of oxygen vacancies resulting from local Ca excess was observed, acting as trap levels promoting longer relaxation pathways. Thanks to the small-sized particles and best steady-state luminescent properties due to a substantial decrease of lattice defects, the HPC synthesis is a promising strategy for light-emitting diode applications. On the other hand, the acetic acid synthesis promoted a higher defect density, which is required for an efficient yield of light emission in the long time range and is thus more suitable for afterglow applications.

Mesoporous titania nanocrystals by hydrothermal template growth

Mesoporous TiO2 nanocrystals have been synthetized by a classical sol-gel route integrated by an hydrothermal growth step using monomeric (dodecylpyridinium chloride, DPC) or dimeric gemini-like (GS3) surfactants as template directing agents. Adsorption isotherms at the solid/liquid interface of the two surfactants have been obtained on aqueous dispersion of titania; the nature of the oxide/adsorbate interactions and the molecules orientation/coarea are discussed. The effects produced by the presence of the two surfactants on the different morphological (surface area, porosity, and shape) and structural (phase composition and aggregate size) features of the final TiO2 samples, calcined at 600°C, are discussed.

Zn- vs Bi-based oxides for o-toluidine photocatalytic treatment under solar light

AbstractThe photodegradation of the highly toxic o-toluidine pollutant was deeply investigated both under UV and solar irradiations by using three different semiconductors: pure ZnO, Bi-impregnated ZnO, and Bi2O3 nanopowders (synthesized by precipitating method). All the samples were deeply characterized on structural, morphological, surface, and optical points of view. The disappearance and the relative mineralization of o-toluidine molecules were followed by linear sweep voltammetry (LSV) and total organic carbon (TOC) determinations, respectively. Hence, correlations between their physico-chemical properties and the photocatalytic performances, passing from UV to solar light, were drawn and a hypothesis on the photodegradation mechanism has been proposed, on the basis of the HPLC/MS results. Bare Bi2O3 samples, due to the exploitation of both their visible light absorption and the negligible intermediates formation, resulted to be higher performing under solar irradiation than either pure or Bi-doped ZnO nanopowders. Graphical abstract