Sergio D’Addato

Structure and stability of nickel/nickel oxide core–shell nanoparticles

The results of a combined x-ray photoelectron spectroscopy (XPS) and high resolution transmission electron microscopy (HR-TEM) study of Ni nanoparticles (NP), before and after oxidation, are presented. An experimental set-up was realized for the preparation and study of pre-formed NP films, concentrating the attention on Ni NP in the diameter range between 4 and 8 nm. The XPS data were taken in situ from NPs after different stages of oxidation, including controlled dosing of O(2) gas in the experimental system and exposure to the atmosphere. The Ni 2p structure is a combination of spectra from metallic Ni in the NP core and from the oxide shell. The signal from the NP core was observed even for samples after exposure to air. From the comparison of HR-TEM experimental images with theoretical simulations, it was found that the Ni NP core has a regular multitwinned icosahedral structure, composed of single-crystal tetrahedra with (111) faces. The NiO phase is clearly observed forming islands on the NP surface.

Evidence of Catalase Mimetic Activity in Ce3+/Ce4+ Doped Bioactive Glasses

The ability of Ce-containing bioactive glasses to inhibit oxidative stress in terms of reduction of hydrogen peroxide, by mimicking the catalase enzyme activity is demonstrated here for the first time. The antioxidant properties of three bioactive glasses containing an increasing amount of CeO2 have been evaluated by following the degradation of hydrogen peroxide with time after immersion in H2O2 aqueous solutions with different concentration. XPS and UV-vis measurements allowed us to determine the Ce(3+)/Ce(4+) ratio in the bulk and on the glass surface, and to correlate it with the ability of the samples to show catalase mimetic activity. Interestingly, we have found that the bioactive glass with composition 23.2Na2O-25.7CaO-43.4SiO2-2.4P2O5-5.3CeO2 immersed in 0.1 M H2O2 aqueous solution is able to degrade 90% of it in 1 week. The reduction in bioactivity of the glasses with increasing CeO2 content is here rationalized in terms of a lower amount of phosphate groups available for the hydroxyapatite layer formation, after binding with cerium ions. In fact, classical molecular dynamics simulations revealed that the addition of CeO2 leads to the formation of cerium phosphate rich regions. The formation of an insoluble CePO4 crystalline phase is also observed by XRD analysis after thermal treatment of the glass samples.

Morphology and magnetic properties of size-selected Ni nanoparticle films

We present the results of a study on the morphology and magnetic properties of size-selected Ni nanoparticles films grown on Si/SiOx substrates. The films were produced by deposition of preformed Ni nanoparticles, using a gas aggregation nanocluster source and an electric quadrupole mass filter. The diameter d of the produced particles ranged between 3 and 10 nm. The morphology of the films, with average thickness t varying from t=0.5 up to t=7 nm, was studied with atomic force microscopy and scanning electron microscopy, combining in this way information about height and lateral topography. We observed the presence of some small aggregates made of two or three particles at the early stage of film formation, probably due to some degree of cluster diffusion on the substrate, and particle average flattening. For increasing values of t, large agglomerates are formed in the films, resulting in a porous structure. Information about the magnetic properties was obtained with field cooled-zero field cooled (FC/ZFC) magnetization curves. We observed a reversibility-irreversibility transition at temperatures 70 K TI, even for the lowest coverage studied (t=2 nm for ZFC/FC measurements, ⟨d⟩=5.5 nm). A comparison with Monte Carlo simulations of the FC/ZFC curves reveals the concurrence between interparticle exchange interaction and single particle random anisotropy.We present the results of a study on the morphology and magnetic properties of size-selected Ni nanoparticles films grown on Si/SiOx substrates. The films were produced by deposition of preformed Ni nanoparticles, using a gas aggregation nanocluster source and an electric quadrupole mass filter. The diameter d of the produced particles ranged between 3 and 10 nm. The morphology of the films, with average thickness t varying from t=0.5 up to t=7 nm, was studied with atomic force microscopy and scanning electron microscopy, combining in this way information about height and lateral topography. We observed the presence of some small aggregates made of two or three particles at the early stage of film formation, probably due to some degree of cluster diffusion on the substrate, and particle average flattening. For increasing values of t, large agglomerates are formed in the films, resulting in a porous structure. Information about the magnetic properties was obtained with field cooled-zero field cooled (FC/ZF...

Influence of defect distribution on the reducibility of CeO2−x nanoparticles

Ceria nanoparticles (NPs) are fundamental in heterogeneous catalysis because of their ability to store or release oxygen depending on the ambient conditions. Their oxygen storage capacity is strictly related to the exposed planes, crystallinity, density and distribution of defects. In this work a study of ceria NPs produced with a ligand-free, physical synthesis method is presented. The NP films were grown by a magnetron sputtering based gas aggregation source and studied by high resolution- and scanning-transmission electron microscopy and x-ray photoelectron spectroscopy. In particular, the influence of the oxidation procedure on the NP reducibility has been investigated. The different reducibility has been correlated to the exposed planes, crystallinity and density and distribution of structural defects. The results obtained in this work represent a basis to obtain cerium oxide NP with desired oxygen transport properties.

Controlled AFM detachments and movement of nanoparticles: gold clusters on HOPG at different temperatures

The effect of temperature on the onset of movement of gold nanoclusters (diameter 27 nm) deposited on highly oriented pyrolytic graphite (HOPG) has been studied by atomic force microscopy (AFM) techniques. Using the AFM with amplitude modulation (tapping mode AFM) we have stimulated and controlled the movement of individual clusters. We show how, at room temperature, controlled detachments and smooth movements can be obtained for clusters having dimensions comparable to or smaller than the tip radius. Displacement is practically visible in real time and it can be started and stopped easily by adjusting only one parameter, the tip amplitude oscillation. Analysing the energy dissipation signal at the onset of nanocluster sliding we evaluated a detachment threshold energy as a function of temperature in the range 300-413 K. We also analysed single cluster thermal induced displacement and combining this delicate procedure with AFM forced movement behaviour we conclude that detachment threshold energy is directly related to the activation energy of nanocluster diffusion and it scales linearly with temperature as expected for a single-particle thermally activated process.

Tunability of exchange bias in Ni@NiO core-shell nanoparticles obtained by sequential layer deposition

Films of magnetic Ni@NiO core-shell nanoparticles (NPs, core diameter d ≅ 12 nm, nominal shell thickness variable between 0 and 6.5 nm) obtained with sequential layer deposition were investigated, to gain insight into the relationships between shell thickness/morphology, core-shell interface, and magnetic properties. Different values of NiO shell thickness t(s) could be obtained while keeping the Ni core size fixed, at variance with conventional oxidation procedures where the oxide shell is grown at the expense of the core. Chemical composition, morphology of the as-produced samples and structural features of the Ni/NiO interface were investigated with x-ray photoelectron spectroscopy and microscopy (scanning electron microscopy, transmission electron microscopy) techniques, and related with results from magnetic measurements obtained with a superconducting quantum interference device. The effect of the shell thickness on the magnetic properties could be studied. The exchange bias (EB) field H(bias) is small and almost constant for ts up to 1.6 nm; then it rapidly grows, with no sign of saturation. This behavior is clearly related to the morphology of the top NiO layer, and is mostly due to the thickness dependence of the NiO anisotropy constant. The ability to tune the EB effect by varying the thickness of the last NiO layer represents a step towards the rational design and synthesis of core-shell NPs with desired magnetic properties.

Morphology, structural properties and reducibility of size-selected CeO2−x nanoparticle films

Summary Non-stoichiometric ceria nanoparticles (NPs) were obtained by a gas aggregation source with a magnetron and were mass-selected with a quadrupole mass filter. By varying magnetron power, Ar gas flow, and the length of the aggregation tube, NPs with an average diameter of 6, 9, and 14 nm were synthesized and deposited onto a substrate, thus obtaining NP films. The morphology of the films was studied with scanning electron microscopy, while high resolution transmission electron microscopy was used to gain a deeper insight into the atomic structure of individual NPs. By using X-ray photoelectron spectroscopy we analyzed the degree of reduction of the NPs of different diameters, before and after thermal treatments in vacuum (reduction cycle) and in O2 atmosphere (oxidation cycle) at different temperatures. From this analysis we inferred that the size is an important parameter only at intermediate temperatures. As a comparison, we evaluated the reducibility of an ultra-thin ceria film with the same surface to volume ratio as the 9 nm diameter NPs film, observing that NPs are more reducible than the ceria film.

Influence of size, shape and core–shell interface on surface plasmon resonance in Ag and Ag@MgO nanoparticle films deposited on Si/SiOx

Summary Ag and Ag@MgO core–shell nanoparticles (NPs) with a diameter of d = 3–10 nm were obtained by physical synthesis methods and deposited on Si with its native ultrathin oxide layer SiOx (Si/SiOx). Scanning electron microscopy and transmission electron microscopy (TEM) images of bare Ag NPs revealed the presence of small NP aggregates caused by diffusion on the surface and agglomeration. Atomic resolution TEM gave evidence of the presence of crystalline multidomains in the NPs, which were due to aggregation and multitwinning occurring during NP growth in the nanocluster source. Co-deposition of Ag NPs and Mg atoms in an oxygen atmosphere gave rise to formation of a MgO shell matrix surrounding the Ag NPs. The behaviour of the surface plasmon resonance (SPR) excitation in surface differential reflectivity (SDR) spectra with p-polarised light was investigated for bare Ag and Ag@MgO NPs. It was shown that the presence of MgO around the Ag NPs caused a red shift of the plasmon excitation, and served to preserve its existence after prolonged (five months) exposure to air, realizing the possibility of technological applications in plasmonic devices. The Ag NP and Ag@MgO NP film features in the SDR spectra could be reproduced by classical electrodynamics simulations by treating the NP-containing layer as an effective Maxwell Garnett medium. The simulations gave results in agreement with the experiments when accounting for the experimentally observed aggregation.

Contraction, cation oxidation state and size effects in cerium oxide nanoparticles

An accurate description of the structural and chemical modifications of cerium oxide nanoparticles (NPs) is mandatory for understanding their functionality in applications. In this work we investigate the relation between local atomic structure, oxidation state, defectivity and size in cerium oxide NPs with variable diameter below 10 nm, using x-ray absorption fine structure analysis in the near and extended energy range. The NPs are prepared by physical methods under controlled conditions and analyzed in morphology and crystalline quality by high resolution transmission electron microscopy. We resolve here an important question on the local structure of cerium oxide NPs: we demonstrate a progressive contraction in the Ce-O interatomic distance with decreasing NP diameter and we relate the observed effect to the reduced dimensionality. The contraction is not significantly modified by inducing a 4%-6% higher Ce3+ concentration through thermal annealing in high vacuum. The consequences of the observed average cation-anion distance contraction on the properties of the NPs are discussed.

Reducible Oxides as Ultrathin Epitaxial Films

This chapter reviews and discusses recent work on two-dimensional films of reducible oxides supported on metal substrates. In general, peculiar chemical and structural phases, different from the bulk ones, can be stabilized depending on the oxygen chemical potential, on kinetic processes and on the specific substrate used. A peculiarity of reducible oxides is that the observed phases can often be reversibly transformed one into the other by applying reducing and oxidizing treatments.