Francesco Pellegrino

On the Simple Complexity of Carbon Monoxide on Oxide Surfaces: Facet-Specific Donation and Backdonation Effects Revealed on TiO2 Anatase Nanoparticles

Atomic-scale relationships between the structure of TiO2 surfaces and the physicochemical properties of surface sites, functional for titania-based applications, can be obtained from IR spectroscopy by using carbon monoxide (CO) as a molecular probe. In the literature, it is reported that strongly unsaturated cationic Ti sites (Lewis acid), which are important for reactivity, should cause a large upshift of the CO stretching frequency. By using IR spectroscopy of CO on TiO2 nanomaterials and theoretical analyses, here this model is challenged. It is shown that the stretching frequency of adsorbed CO results from a facet-dependent and synergic CO-surface donation (upshift) - surface-CO backdonation (downshift) mechanism. These results imply that the interaction of adsorbed molecules with the Ti centers is tuned by the surface oxygen atoms of the first coordination sphere, which play an active role as indirect electron density donors (Lewis base).

BaCO3 and NH3SO3 as Precursors for the Hydrothermal Synthesis of BaSO4

In this study, we demonstrated that BaCO3 and NH3SO3 can be conveniently used as BaSO4 precursors. BaSO4 is obtained by treating the precursor, BaCO3, with a sulfate-containing solution, owing to the lower solubility product constant of BaSO4 compared to that of BaCO3. Using this procedure, BaSO4 particles with pseudo-cubic/prismatic morphology are obtained. In this case, temperature and reaction time have little influence on morphology, which is mainly controlled by supersaturation and sulfate concentration. Sulfate counter ion also affects the morphology, but its effect is less pronounced. The hydrolysis of NH3SO3 in the presence of soluble barium salts produces BaSO4 particles, and different kinds of morphology can be obtained, encompassing rounded and nearly spherical particles, prismatic and pseudo-cubic, irregular shapes with flat and well-developed facets, and even hopper crystals. In these syntheses, temperature and pH are playing a major role in controlling sulfamic acid hydrolysis and, therefore, supersaturation, with remarkable consequences for crystal nucleation and growth. Considering that BaSO4 finds applications in many sectors and for different purposes, the variety of particle size and shape reported in this study can potentially improve the performance of the materials in which BaSO4 particles are employed.

Beyond Shape Engineering of TiO2 Nanoparticles: Post-Synthesis Treatment Dependence of Surface Hydration, Hydroxylation, Lewis Acidity and Photocatalytic Activity of TiO2 Anatase Nanoparticles with Dominant {001} or {101} Facets

TiO2 anatase nanoparticles are among the relevant players in the field of light-responsive semiconductor nanomaterials used to face environmental and energy issues. In particular, shape-engineered TiO2 anatase nanosheets with dominant {001} basal facets gained momentum because of the possibility to exploit different and/or improved functional behaviors with respect to usual bipyramidal TiO2 anatase nanoparticles, mainly exposing {101} facets. Nevertheless, such behavior depends in a significant extent on the physicochemical features of surfaces exposed by nanosheets. They can vary in dependence on the presence or removal degree of capping agents, namely, fluorides, used for shape-engineering, and experimental investigations in this respect are still a few. Here we report on the evolution of interfacial/surface features of TiO2 anatase nanosheets with dominant {001} facets from pristine nanoparticles fluorinated both in the bulk and at their surface to nanoparticles with F– free surfaces by treatment in a ...

Analysis of fluorine traces in TiO2 nanoplatelets by SEM/EDX, AES and TOF-SIMS

Hydrothermal synthesis of anatase TiO2 nanosheets with a high fraction of exposed {001} facets and related high photocatalytic activity - as an alternative to bipyramidal anatase TiO2 nanoparticles mainly exposing the {101} facets. The scope of the material preparation work is the thermal reduction of residual fluorides from HF (capping agent) induced during the synthesis of TiO2 nanosheets by calcination at 873K. The analytical task consists of detection and localization of fluorine present at the surface and/or in the bulk of TiO2 nanosheets before and after calcination by SEM/EDX, Auger electron spectroscopy and ToF-SIMS.