Matteo Redaelli

Efficacy of the Reactive Oxygen Species Generated by Immobilized TiO2 in the Photocatalytic Degradation of Diclofenac

We report on the photodegradation of diclofenac (DCF) by hydrothermal anatase nanocrystals either free or immobilized in porous silica matrix (TS) in connection to the type and amount of reactive oxygen species (ROS), in order to have deeper insight into their role in the photocatalysis and to provide an effective tool to implement the DCF mineralization. TiO2 and TS exhibit a remarkable efficiency in the DCF abatement, supporting that the utilization of anatase nanoparticles with the highly reactive , , and exposed surfaces can be an effective way for enhancing the photooxidation even of the persistent pollutants. Furthermore, the hydrothermal TiO2, when immobilized in silica matrix, preserves its functional properties, combining high photoactivity with an easy technical use and recovery of the catalyst. The catalysts performances have been related to the presence of OH•, , and species by electron paramagnetic resonance spin-trap technique. The results demonstrated that the ROS concentration increases with the increase of photoactivity and indicated a significant involvement of in the DCF degradation. The efficacy of TiO2 when immobilized on a silica matrix was associated with the high ROS life time and with the presence of singlet oxygen, which contributes to the complete photomineralization of DCF.

Hybrid SiO2@POSS nanofiller: a promising reinforcing system for rubber nanocomposites

A novel hybrid nanofiller, SiO2@POSS, where the silica nanoparticles (NPs) and the POSS belong to the same functional structure, has been synthesized by grafting different loadings of OctaMethacrylPOSS onto silanized commercial SiO2, using a surface reaction mediated by dicumylperoxide (DCP). The peroxide, besides anchoring the nanocages onto the silica surface, ensures the presence of methacryl functionalities in the final structure, which are still available for cross-linking reactions with a polymer host. The hybrid SiO2@POSS NPs were used to prepare, by ex situ blending, SBR nanocomposites. The dynamic-mechanical analysis performed on the cured SBR/SiO2@POSS composites indicated that the presence of POSS induces a remarkable increase of modulus either at low or at high strain, and a considerable decrease of hysteresis. This has been associated with the peculiar hybrid structure of the SiO2@POSS filler, in which silica NP aggregates are partially interconnected and surrounded by a thin shell of POSS nanounits which, thanks to their high number of reactive functionalities, promote the formation of “sticky regions” among the silica aggregates and, consequently, a tight filler network wherein rubber is immobilized. This grants a relevant reinforcement and increased hysteretic properties, suggesting SiO2@POSS as a promising filler system for decreasing the energy loss under strain and for leading to a potential reduction of filler utilization in rubber composite formulations.

New insights into the sensing mechanism of shape controlled ZnO particles

The sensing behavior of pyramidal (PY), prismatic hexagonal (EP) and hexagonal rod-like (ER) ZnO micro and sub-microparticles, has been compared with that of commercial ZnO (ZnO®) particles having nanometric size and uneven shape. The performances have been firstly related to the predominance of specific crystal surfaces and then, more in depth, to the paramagnetic defects in ZnO ( and ), detected by Electron Spin Resonance (ESR), in order to associate the particles morphology with the defects amount and reactivity and, in turn, with a particular sensing mechanism. The results showed that the sensing behavior of ZnO® containing irregular nanoparticles is essentially related to the alternate formation and filling of oxygen vacancies during the gas pulse (oxygen vacancy mechanism), while that of ER and EP crystals does not seem to directly involve the defects. In particular, the sensing properties of shape controlled ZnO particles are mainly attributed to the ability of (0001) exposed surfaces in favoring a far better chemisorption of negatively charged oxygen species, then available for the reactions with the reducing gas (i.e. ionosorption mechanism). The outcomes and the approach adopted in this study may positively contribute to the debate still existing between the oxygen vacancy and ionosorption models by giving indications on the predominance of a specific sensing mechanism in shape controlled ZnO.

Unveiling the hybrid interface in polymer nanocomposites enclosing silsesquioxanes with tunable molecular structure: Spectroscopic, thermal and mechanical properties

Organic-inorganic nanobuilding blocks (NBBs) based on silsesquioxanes (SSQs) have potential applications as nanofillers, thermal stabilizers, and rheological modifiers, which can improve thermomechanical properties of polymer hosts. The possibility to tune both siloxane structure and pendant groups can promote compatibilization and peculiar interactions with a plethora of polymers. However, the control on SSQs molecular architecture and functionalities is usually delicate and requires careful synthetic details. Moreover, investigating the influence of NBBs loading and structure on the hybrid interface and, in turn, on the polymer chains mobility and mechanical properties, may be challenging, especially for low-loaded materials. Herein, we describe the preparation and characterization of polybutadiene (PB) nanocomposites using as innovative fillers thiol-functionalized SSQs nanobuilding blocks (SH-NBBs), with both tailorable functionality and structure. Swelling experiments and, more clearly, solid-state NMR, enlightened a remarkable effect of SH-NBBs on the molecular structure and mobility of the polymeric chains, envisaging the occurrence of chemical interactions at the hybrid interface. Finally, thermal and DMTA analyses revealed that nanocomposites, even containing very low filler loadings (i.e. 1, 3 wt%), exhibited enhanced thermomechanical properties, which seem to be connected not only to the loading, but also to the peculiar cage or ladder-like architecture of SH-NBBs.

Synthesis and Characterization of Morphology-Controlled TiO2 Nanocrystals: Opportunities and Challenges for their Application in Photocatalytic Materials

Abstract 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 TiO 2 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 TiO 2 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 TiO 2 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 TiO 2 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 TiO 2 NCs in smart materials will be proposed.