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Abstract: We report the synthesis, characterization and relaxometric study of ferrofluids based on iron oxide, with potential for use as magnetic resonance imaging (MRI) contrast agents (CAs). The effect of different cost-effective, water-based surface modification approaches which can be easily scaled-up for the large scale synthesis of the ferrofluids has been investigated. Surface modification was achieved by silanization, and/or coating with non-toxic commercial dispersants (a lauric polysorbate and a block copolymer with pigment affinic groups, namely Tween 20 and Disperbyk 190) which were added after or during iron oxide nanoparticle synthesis. It was observed that all the materials synthesized functioned as negative contrast agents at physiological temperature and at frequencies covered by clinical imagers. The relaxometric properties of the magnetic nanoparticles were significantly improved after surface coating with stabilizers compared to the original iron oxide nanoparticles, with particular reference to the silica-coated magnetic nanoparticles. The results indicate that the optimization of the preparation of colloidal magnetic ferrofluids by surface modification is effective in the design of novel contrast agents for MRI by enabling better or more effective interaction between the coated iron oxide nanoparticles and protons present in their aqueous environment. [Copyright &y& Elsevier]

[Display omitted] • CNT supported Ru single atoms have been associated to Ru, Pd and Ni particles. • Hydrogen spillover induced a cooperative catalysis between supported Pd and Ni particles and Ru single atoms. • The RuNi/CNT catalyst contains a cocktail of catalytic species including isolated Ru single atoms and Ru single atoms on Ni particles. • The RuNi/CNT catalyst shows much better performances in terms of activity and selectivity compared to the monometallic systems. • DFT calculations revealed that the active species is a Ru SA @Ni NP single atom alloy. Reaching high selectivity at high conversion and high rate in the industrially important selective hydrogenation of α,β-unsaturated aldehydes is a challenging task. Among current approaches reported in the literature, high selectivity towards the unsaturated alcohol or saturated aldehyde is generally achieved at the expense of activity. The use of bimetallic systems can lead either to selectivity or to activity enhancement, but generally not to both. Herein, we show that, for cinnamaldehyde hydrogenation, combining Ni nanoparticles (Ni NP) and Ru single atoms (Ru SA) on CNTs allows improvement of the hydrocinnamaldehyde selectivity, while obtaining a remarkable activity. The STY of Ru SA -Ni NP /CNT is approximately 60 times higher than that of the Ru SA /CNT and 10 times higher than that of the Ni NP /CNT. Importantly, the resulting catalyst shows 94% selectivity at 99% conversion and a good stability in flow. Insights into the cooperative "cocktail"-type catalysis between Ni NP and Ru SA were revealed from density functional theory calculations. [ABSTRACT FROM AUTHOR]

Abstract: The influence of PtRu bimetallic particle size and composition on cinnamaldehyde selective hydrogenation has been investigated for the first time using well-defined catalysts based on carbon nanotubes support. Very high selectivity towards cinnamyl alcohol together with high activity have been obtained provided a high temperature treatment of the catalyst is performed. HRTEM, WAXS and EXAFS analyses permit us to conclude that the remarkable influence of this high temperature treatment on both activity and selectivity arises from different phenomena. First, a particle size and a structural effect have been evidence that permits to increase the selectivity. WAXS and EXAFS point the formation of alloyed PtRu nanoparticles. Second, the heat treatment allows the removal of oxygenated groups from CNT surface. This may increase the cinnamaldehyde adsorption capacity and decrease the activation barrier for diffusion of substrate and product on the CNT surface, thus contributing to an increase in the activity. [Copyright &y& Elsevier]

Surfactant-mediated chemical routes allow one to synthesize highly engineered shape- and size-controlled nanocrystals. However, the occurrence of capping agents on the surface of the nanocrystals is undesirable for selected applications. Here, a novel approach to the production of shape-controlled nanocrystals which exhibit high thermal stability is demonstrated. Ceria nanocubes obtained by surfactant-mediated synthesis are embedded inside a highly porous silica aerogel and thermally treated to remove the capping agent. Powder X-ray Diffraction and Scanning Transmission Electron Microscopy show the homogeneous dispersion of the nanocubes within the aerogel matrix. Remarkably, both the size and the shape of the ceria nanocubes are retained not only throughout the aerogel syntheses but also upon thermal treatments up to 900 °C, while avoiding their agglomeration. The reactivity of ceria is measured by in situ High-Energy Resolution Fluorescence Detected - X-ray Absorption Near Edge Spectroscopy at the Ce L 3 edge, and shows the reversibility of redox cycles of ceria nanocubes when they are embedded in the aerogel. This demonstrates that the enhanced reactivity due to their prominent {1 0 0} crystal facets is preserved. In contrast, unsupported ceria nanocubes begin to agglomerate as soon as the capping agent decomposes, leading to a degradation of their reactivity already at 275 °C. [ABSTRACT FROM AUTHOR]

The structure of the iron oxyhydroxide called feroxyhyte (δ-FeOOH), which shows an elusive X-ray powder diffraction pattern, has been represented so far using models describing a mean structure based on the crystalline network of the iron(III) oxide hematite (α-Fe 2 O 3 ). In this paper, a novel description of the mean structure of feroxyhyte is presented, which is based on the structure of the thermodynamically stable iron oxyhydroxide goethite. Starting from different local arrangements present in the goethite network, a mean structural model is determined which shows an X-ray powder diffraction pattern almost coincident with previous studies. This outcome enables to integrate the structure of feroxyhyte among those of other well characterized iron oxyhydroxides. [ABSTRACT FROM AUTHOR]