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In the present work, novel ceria-based nanocatalysts containing different quantities of La and Nd were prepared via hydrothermal synthesis. The effects of doping on the structural and physico-chemical properties of ceria were examined with several techniques, such as XRD, FESEM, TEM, Raman spectroscopy, XPS, H 2 -TPR and O 2 /NH 3 /CO 2 -TPD. The catalytic activity of doped ceria towards CO, NO and soot oxidation was evaluated in different conditions; in particular, the role of the catalyst-soot contact and the influence of NO x and water on the soot oxidation performances were investigated. La and Nd ions were well incorporated in ceria structure, but the final morphology was significantly altered. The introduction of trivalent cations was also associated with a higher abundance of defects and oxygen vacancies, but an excessive oxygen deficiency detrimentally affected the material reducibility and catalytic activity for CO and NO oxidation. Conversely, soot oxidation benefited from La and Nd addition. In particular, the Ce-La equimolar oxide exhibited outstanding performances in all the tested conditions, thanks to its optimal morphology and surface acidity. A detailed comparison with equimolar ceria-praseodymia allowed to investigate how acid-base sites and redox properties control the different catalytic mechanisms involved in standard and NO x -assisted soot oxidation. [Display omitted] • La and Nd ions can be well incorporated in the lattice of ceria-based nanocatalysts. • Excessive oxygen deficiency and defectiveness negatively affect ceria reducibility. • Equimolar ceria-lanthana shows an outstanding activity towards soot oxidation. • Acid-base sites strength is closely related to doped ceria catalytic performances. • Different NO x -assisted soot oxidation pathways are promoted by La or Pr doped ceria. [ABSTRACT FROM AUTHOR]

• CO oxidation was studied by in situ Raman spectroscopy on nanostructured ceria-based materials. • In situ Raman analyses during CO oxidation allowed to monitor defect sites in operando conditions. • Cycles of reduction (CO in N 2) and oxidation (pure O 2) at 400 °C allow to study the stability of defects. • Oxygen vacancies evolved from clusters to isolated ones according to the atmosphere and temperature. • The involvement of the defect sites in structural rearrangement is fostered by easily reducible dopants. Among the factors affecting ceria activity, the defectiveness plays a key role in the case of CO oxidation. In this study, its connection with the catalytic performance was investigated via in-situ Raman spectroscopy on nanostructured pure and Cu/Mn-doped ceria, monitoring the defect sites and surface species evolution during the reaction. The accumulation of polyene-like chains, formed through CO dissociative adsorption at the catalyst surface, was observed and their disappearance was related to the catalyst light-off temperature. Moreover, the doped samples exhibited a rise of the Raman bands associated to defects after the tests, consequence of the structural rearrangements occurring during CO oxidation. Indeed, in-situ Raman measurements during reduction (CO/N 2) and oxidation cycles at 400 °C evidenced the formation of oxygen vacancy clusters in reducing atmosphere, which could reorganize not only in O 2 but also upon a temperature decrease, forming isolated vacancies and then evolving in Frenkel and extrinsic oxidized dopant-containing sites when exposed to oxygen. [ABSTRACT FROM AUTHOR]

Osteoporosis (OP) is a skeletal disorder responsible for the weakening of the bone structure and, consequently, for an increased fracture risk in the elderly population. In the past, bone mineral density (BMD) variation was considered the best OP indicator, but recently the focus has shifted toward the variation of microstructural bone parameters. This work is based on the characterisation of 8-mm cylindrical biopsies harvested from proximal humeral heads belonging to healthy and osteoporotic patients, in order to assess the OP-related variations of bone properties at different scale lengths. In particular, bone biopsies underwent micro-computed tomography analysis to study the most relevant features of bone architecture and extrapolate the tissue mineral density (TMD) value of bone trabeculae. Compression tests and nanoindentations were performed to investigate the macro- and micromechanical properties of bone biopsies, respectively. In addition, XRD analyses were performed to obtain the mean hydroxyapatite (HA) crystallite size, while Raman spectroscopy investigated the collagen secondary structure. Thermogravimetric analysis was performed to evaluate the ratio between organic and inorganic phases. From the obtained results, OP samples showed a more anisotropic and less interconnected structure responsible for reduced compression strength. From this, it can be supposed that OP caused an alteration of bone structure that led to inferior macroscopic mechanical properties. Furthermore, OP samples possessed higher TMD and bigger HA crystals that are correlated to an increase of the hardness value obtained by means of nanoindentation. This less controlled HA crystal growth is probably due to an alteration of the organic matrix structure, as revealed by the increase of the random coil contribution in the Raman spectra of the OP bone. This higher crystal content led to an increase in trabecular density and hardness. In conclusion, the obtained data showed that OP affects bone properties at different scale lengths causing an alteration of its morphological, structural and mechanical features. Image 1 • OP bone shows an altered trabecular structure withstanding lower compressive loads. • OP bone has bigger HA crystals that lead to increased TMD and hardness values. • A modified collagen structure is found in OP bone causing the altered growth of HA. • Correlation exists between bone macroscopic properties and its microscopic features. [ABSTRACT FROM AUTHOR]

Catalytic oxidation is the most effective technology to control methane emissions from both mobile and stationary sources. Palladium-based materials are widely viewed as the most active catalysts for the methane abatement reaction, even though the high-temperature PdO/Pd transition is linked to a decrease in catalytic activity. Aimed at minimizing this phenomenon, this work compares the catalytic activity and the thermal stability of different Pd-impregnated cerium-praseodymium mixed oxides prepared via Solution Combustion Synthesis. Although the palladium deposition on pure ceria allows obtaining a highly active system, the introduction of praseodymium enhances the thermal stability of the catalyst in an extended temperature range. X-ray photoelectron spectra show that the presence of praseodymium retains Pd in a more oxidized form, thus stabilizing the high-temperature active phase. This effect, as evident from X-ray diffractograms and Raman analyses, was attributed to a strong interaction of palladium particles with praseodymium, thereby hindering their reduction to the metallic form. Moreover, Pr doping played a significant role during methane oxidation in the presence of 5% H 2 O, improving both activity and stability compared to Pd on pure ceria. On the whole, Pd/Ce90Pr10 (2 wt% palladium supported on a mixed oxide with a praseodymium content of 10% on a cerium-praseodymium molar basis) was found to be the most promising catalyst amongst the studied materials in both dry and wet conditions, benefitting from the synergistic effect of ceria and praseodymia in improving the Pd activity and stability. [Display omitted] • Pd-impregnated Ce-Pr mixed oxides were studied for complete methane oxidation. • Small amounts of Pr proved to be crucial for obtaining an active and stable system. • The system stability was related to strong Pd-Pr interactions. • Pd/Ce90Pr10 was found as the most active sample in both dry and wet condition tests. [ABSTRACT FROM AUTHOR]

The need to deliver high performant and miniaturised electrochemical sensors has boosted the use of carbon nanomaterials as smart modifiers of working electrode surface. Among the carbon nanomaterials, the common and cost-effective carbon black has recently attracted the attention from the scientific community for its outstanding features as electrode nanomodifier for analyte detection. Herein, we report the structural and morphological characterisation of several types of carbon blacks, namely HP 160, HS20, MTN 990, N115, N220, N375, N660, PL6, Super P, and XE2B, by means of Raman spectroscopy, transmission electron microscopy (TEM) and scanning electron microscopy (SEM) analyses. Furthermore, the electrochemical characterisation of screen-printed electrodes modified with these carbon blacks was carried out by cyclic voltammetry and electrochemical impedance spectroscopy with ferro/ferricyanide as redox probe, highlighting the advantage to use carbon black as nanomodifier in respect to the bare electrode. Among several tested carbon black types, the lowest peak-to-peak separation and resistance to electron transfer values were achieved using screen-printed electrodes modified with CB N115, N375, HP 160 and PL6. The electrodes modified with these types of CB were successively tested in cyclic voltammetry towards epinephrine, benzoquinone, ascorbic acid, cysteine, catechol, and caffeic acid, observing a remarkable improvement of electrochemical performances in respect to the bare electrode, even when the amperometric mode was used. The results obtained demonstrated that several types of CB can remarkably improve the electrochemical performances of the sensors in terms of the decrease of applied potential or peak-to-peak separation, the improvement of the peak intensity, and the decrease of the resistance of the electron transfer due to several key features, including nanodimensions, the onion-like carbon structure, and the high number of defect sites. Image 1 [ABSTRACT FROM AUTHOR]