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Biocomposites based on sepiolite (Sep) clays and natural rubber latex (NRL) are novel green synthetic materials with significant mechanical performance obtained by an eco-friendly and sustainable mixing procedure, without the use of surfactants. In this work, experiments and theory are combined to investigate the stability of colloidal dispersions formed by a mixture of both negatively charged Sep fibers and non-adsorbing NRL particles. Experiments were performed by adding Sep fibers to NRL dispersions with different Sep/NRL volume fractions to evaluate the effect of Sep dispersion and NRL loading on the flocculation process. In order to theoretically understand the experimental results on colloidal stability, a density functional approach was applied to calculate the depletion interaction between two Sep fibers induced by the presence of naturally charged NRL, and an effective one-component mean-field free energy was developed to predict the phase behavior of the Sep/NRL mixture. The existence of a depletion attraction, enhanced by the electrostatic repulsion between Sep and NRL, is shown to be strong enough to induce the flocculation of the mixture at determined Sep and NRL volume fractions. The theoretical predicted phase diagram is in excellent qualitative and quantitative agreement with the experimental results, indicating that this electrostatically-enhanced depletion effect plays a key role in the colloidal stability of this system. To the best of our knowledge, this study represents the first attempt to tackle how depletion effects can be exploited to produce and control Sep/NR biocomposites.

Morphology-controlled titania nanocrystals (NCs) are indicated as promising building blocks for the generation of new photocatalytic materials, where precise tailoring of particle size and exposed crystal surfaces enables to fulfill specific reactivity requirements. In fact, beyond the dimensions, the presence of different TiO2 facets dramatically affects its photoactivity. This has been recently connected to the peculiar electronic band structures of specific surfaces and to their ability in promoting the concentration of different photogenerated defects. The most mature methods for the synthesis of shape-controlled TiO2 utilize organic surfactants, which commonly remain anchored to the NCs surfaces, often precluding their final use in photocatalytic applications. Although several alternatives have been provided (e.g., ligand exchange), there is still an urgent need to identify approaches for controlling morphology by also granting tunable surface functionalities, easy scalable procedures, and applicability in "friendly" materials (e.g., pellet, membranes, or flexible substrates). Bearing these challenges in mind, this chapter briefly presents the basic synthesis strategies for tuning morphology and surfaces of TiO2 NCs, focusing on those that may guarantee a transfer of the NCs intrinsic features to technological applicable photocatalytic materials. A brief state of art of the microscopic and spectroscopic techniques utilized for verify and study their morphology-dependent functionalities will be described. In this context and aiming to suggest implementation of TiO2 reactivity, a special attention will be devoted to spectroscopies (mainly ESR) allowing to monitor quasi "in situ" the photocatalytic mechanism. Finally, some perspectives for the inclusion of shape-controlled TiO2 NCs in smart materials will be proposed.

The present study reports on the preparation and characterization of innovative "self-cleaning" nano-TiO2 treatments to be used in cultural heritage, based on dispersion of solar-light activated TiO2 nanocrystals. The semiconductor has been prepared by an easy and low-cost non-aqueous procedure, providing anatase (NA_TiO2) nanoparticles photo-active not only under UV-light but also under solar irradiation. NA_TiO2 allows obtaining very stable dispersions either in water or in ethylene glycol used to produce homogeneous nano-TiO2 treatments on Noto stone and Carrara marble, which display excellent aesthetic compatibility, do not remarkably affect the capillary water absorption of the stones and slightly increase their wettability.The new treatment exhibits higher photocatalytic activity compared to that based on commercial TiO2 (P25_TiO2). This behavior has been attributed not only to the morphological properties of the treatments and of the stones, but also to the presence of residual benzyl alcohol molecules anchored on the anatase NP surfaces. This provides solar light absorption and partially improves the charge trapping, thus increasing the photoefficiency. The overall results suggest that the positive combination of high dispersion, solar-light absorption and reduced recombination effects in NPs plays a key role in the development of efficient photocatalytic treatments for stone restoration.