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Multifunctional materials working under solely visible-light are expected to play a significant role in photo-electronics, in particular photo-switches, photo-optical sensors, smart windows, displays, optical storage memories, and self-cleaning materials. We have modified the surface of a versatile semiconductor material (TiO2) with a noble metal (copper) and high crystalline quality graphene. Exploiting the ability of a semiconductor to generate an exciton upon excitation, a multifunctional material working with visible-light and showing photochromic and photocatalytic activity was engineered. Photochromic and photocatalytic tests were assessed using a white light emitting diode (LED). Specimens modified with copper (1 mol%) and graphene (0.5 wt%) exhibited faster photochromism (3 times), and more stable photoswitching compared to standard Cu-TiO2 photochromic material. The same material also displayed visible-light induced photocatalytic activity in the gas-solid phase (degradation of benzene, one of the most hazardous pollutants found indoor) superior to unmodified titania (3.00 times higher). Copper acted as the chromophore (and visible-light absorber for the photocatalytic reaction). Furthermore, the electronic transport is enhanced in the graphene/TiO2 hybrids, increasing the lifetime of the photogenerated exciton. Our data highlights the unique characteristics of that material, and the suitability for multi-purpose applications in the field of environmental monitoring and remediation, and smart materials technologies.

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This thesis wad aimed at the study and application of titanium dioxide photocatalytic activity on ceramic materials. As a matter of fact, photocatalysis is a very promising method to face most of the problems connected with the increasing environmental pollution. Furthermore, titanium dioxide, in its anatase crystallographic phase, is one of the most investigated photocatalytic material and results to be perfectly compatible with silicate body mixes. That goal was pursued by two different strategies: 1. the addition to a body mix used for heavy clay products of several titania powders, with different mean crystallite size, surface area, morphology and anatase/rutile ratio and a titania nanosuspension as well. The titania addition followed two procedures: bulk and spray addition over the ceramic samples surface. Titania was added in two different percentages: 2.5 and 7.5 wt.% in both of the methods. The ceramic samples were then fired at three maximum temperatures: 900, 950 and 1000 °C. Afterwards, the photocatalytic activity of the prepared ceramic samples was evaluated by following the degradation of an organic compound in aqueous medium, under UV radiation. The influence of titania morphological characteristics on the photoactivity of the fired materials was studied by means of XRD and SEM observations. The ceramic samples, sprayed with a slip containing 7.5 wt.% of titania powder and fired at 900 °C, have the best photoactivity, with a complete photo-decomposition of the organic compound. At 1000 °C no sample acted as a photocatalyst due to the anatase-to-rutile phase transformation and to the reaction between titania and calcium and iron oxides in the raw materials. 2. The second one foresaw the synthesis of TiO2-SiO2 solid solutions, using the following stoichiometry: Ti1-xSixO2 where x = 0, 0.1, 0.3 and 0.5 atoms per formula unit (apfu). The mixtures were then fired following two thermal cycles, each with three maximum temperatures. The effect of SiO2 addition into the TiO2 crystal structure and, consequently, on its photocatalytic activity when fired at high temperature, was thoroughly investigated by means of XRD, XPS, FE-SEM, TEM and BET analysis. The photoactivity of the prepared powders was assessed both in gas and liquid phase. Subsequently, the TiO2-SiO2 solid solutions, previously fired at 900 °C, were sprayed over the ceramic samples surface in the percentage of 7.5 wt.%. The prepared ceramic samples were fired at 900 and 1000 °C. The photocatalytic activity of the ceramic samples was evaluated in liquid phase. Unfortunately, that samples did not show any appreciable photoactivity. In fact, samples fired at 900 °C showed a pretty low photoactivity, while the one fired at 1000 °C showed no photoactivity at all. This was explained by the excessive coarsening of titania particles. To summarise, titania particle size, more than its crystalline phase, seems to have a relevant role in the photocatalytic activity of the ceramic samples.

Lime slaker grits and biomass fly ash are solid wastes produced by the Kraft paper-pulp industry that are commonly disposed of in landfill. However, recent studies and European regulations discourage such disposal practices. This work investigates an alternative and innovative way to recycle and reuse these wastes in the production of green geopolymeric mortars intended for application in the construction industry. Here, biomass fly ash was used as the main source of alumino-silicate in the binder precursor (70 wt.% substitution to metakaolin), and grits (ranging from 1&ndash, 12.5 mm, as provided by the industry) were reused as aggregate. Aggregate granulometry was also completed by using a commercial natural siliceous sand (&lt, 1 mm). Mortars using sand only were prepared for comparative reasons. The implemented mix was designed to investigate the influence of the grits on the mortar&rsquo, s properties such as its binder/aggregate ratio, workability, bulk density, water sorptivity, and compressive strength. At the same time, waste reuse was analysed in light of its limitations and potentialities. Moreover, in the pursuit of sustainability, the manufacturing process that was followed was highly cost-effective in ambient curing conditions (20 &deg, C, 65% RH), which avoided the use of any external source of energy as commonly used in geopolymers processing. The achieved results proved that the combined use of these wastes, which to date has hardly been explored, along with ambient manufacturing conditions increases the material sustainability. The produced mortars are suitable for innovative applications in various fields, with a particular focus on construction and contribute to the circular economy.